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  • Organic Chemistry  (4,740)
  • Life and Medical Sciences  (4,281)
  • 1995-1999  (6,606)
  • 1930-1934  (2,415)
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  • 101
    Electronic Resource
    Electronic Resource
    Stereoselective Synthesis of 2,4,6-Trimethylcyclohex-4-ene-1,3-diol Derivatives and of polypropionate fragments with four contiguous stereogenic centersFor a preliminary report, see [1]. (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 325-343 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Diels-Alder adduct (±)-3 of 2,4-dimethylfuran and 1-cyanovinyl acetate was converted stereoselectively into benzyl 6-(4-chlorophenylsulfonyl)-1,3-exo,5-trimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-exo-yl (26) and -2-endo-yl ether (36). Addition of LiAlH4 to the latter led to the 3-O-benzyl derivatives 28 and 37 of (1RS,2SR,3SR,6SR)- and (1RS,2SR,3RS,6SR)-5-(4-chlorophenylsulfonyl)-2,4,6-trimethylcyclohex-4-ene-1,3-diol, respectively. Methylenation of 6-exo-(4-chlorophenylthio)-1-methyl-5-methylidene-7-oxabicyclo[2.2.1]heptan-2-one (16), obtained by reaction of (±)-3 with 4-Cl-C6H4SCl and saponification gave, 6-exo-(4-chlorophenylthio)-1-methyl-3,5-dimethylidene-7-oxabicyclo [2.2.1]heptan-2-one (43), the reduction of which with K-Selectride afforded 6-exo-(4-chlorophenylthio)-1,3-endo-dimethyl-5-methylidene-7-oxabicyclo[2.2.1]heptan-2-endo-ol (44). The 3-O-benzyl derivative 48 of (1RS,2RS,3RS,6SR)-5-(4-chlorophenylsulfonyl)- 2,4,6-trimethylcyclohex-4-ene-1,3-diol was derived from 44 via based-induced oxa-ring opening of benzyl 6-endo-(4-chlorophenylsulfonyl)-1,3-endo-5-endo-trimethyl-7-oxabicyclo[2.2.1]hept-2-endo-yl ether (49). Benzylation of 28, followed by reductive desulfonylation and oxidative cleavage of the cyclohexene moiety afforded (2RS,3SR,4RS,5RS)-3,5-bis(benzyloxy)-2,4-dimethyl-6-oxoheptanal (32).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19950780206
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  • 102
    Electronic Resource
    Electronic Resource
    Synthesis of a Novel Tricyclic Dipeptide Template and Its Incorporation into a Cyclic Peptide Mimetic Containing an NPNA Motif (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1513-1527 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel tricyclic dipeptide template, formally derived by coupling (2S,4S)-4-aminoproline (Pro(NH2)) and (S)-2-(carboxymethyl)proline (Pro(CH2COOH)) as a diketopiperazine, has been synthesized in a form suitable for solid-phase peptide synthesis using Fmoc chemistry. This template was incorporated into the cyclic molecule cyclo(-Ala1-Asn2-Pro3-Asn4-Ala5-Ala6-Temp-) (Temp = template), whose conformation in H2O was studied by NMR methods. Average solution structures derived by restrained simulated annealing point to a highly populated βI-turn within the Asn-Pro-Asn-Ala motif and also indicate which conformations are likely to be preferred by the template.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800514
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  • 103
    Electronic Resource
    Electronic Resource
    Aza-Claisen Rearrangement: Synthesis of 5′-branched 5′-aminothymidinesDedicated with best personal wishes of D. B. to Professor Oskar Jeger on the occasion of his 80th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1589-1606 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of both diastereoisomers of 5′-ethyl-substituted thymidine dimers, the (5′R)- and (5′S)-configurated 33a and 33b respectively, in which the natural phosphodiester linkage is replaced by an amide group (C(3′)-CH2CONH-CH(5′)(Et)), arc described. Their fully protected derivatives 35a and 35b, respectively, are suitable for incorporation into antisense oligonucleotides. Unexpectedly, an attempted PdII-catalysed aza-Claisen rearrangement of trichloroacetimidate 7 provided the diastereoisomerically pure cyclopropane derivative 17, whose structure was confirmed by X-ray analysis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800517
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  • 104
    Electronic Resource
    Electronic Resource
    Neue Wege zu Pentalen-Vorstufen17. Mitteilung über Kupplungsreaktionen 16. Mitteilung (Kurzmitteilung): [1] (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1627-1638 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Pathways to Precursors of PentalenePentalene dimers 2 and 3 are easily available in moderate yields by CuCl2-induced oxidative coupling of dilithium-pentalenediide (5) (Scheme 1). On the other hand, NBS bromination of 1,5-dihydropentalene (4) or of 1,2-dihydropentalene (8) gives unstable 1-bromo-1,2-dihydropentalene (9), while subsequent in-situ elimination with Et3N exclusively gives syn-cis-pentalene dimer 2 in moderate yields (Scheme 3). NMR-Spectroscopic evidence for compounds 2, 3, and 9 is presented, and mechanistic alternatives for the formation of pentalene dimers 2 and 3 are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800520
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  • 105
    Electronic Resource
    Electronic Resource
    Masthead (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997) 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800601
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  • 106
    Electronic Resource
    Electronic Resource
    Iridoid Glucosides with Free Radical Scavenging Properties from Fagraea blumei (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1144-1152 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new iridoid glucosides 1-4, named blumeosides A-D, were isolated from the methanolic stem-bark extract of Fagraea blumei G. DON. (Loganiaceae). They were accompanied by the benzyl-alcohol derivative di-O-methylcrenatin (5) and the flavone C-glucoside swertisin (6). The structures of 1-4 were established by spectroscopic methods, including FAB-MS, and 1H- and 13C-NMR, and by alkaline hydrolysis. Blumeosides A (1) and C (3) are 10-O-(2,5-dihydroxytercphthalo) adoxosidic acid and 10-O-(2-hydroxyterephthalo)adoxosidic acid, respectively. In blumeosides B (4) and D (2), both carboxylic groups of the terephthalic-acid moiety are esterified by adoxosidic-acid units, Blumeosides A-D (1-4) inhibited bleaching of crocin induced by alkoxyl radicals. Blumeosides A (1) and D (2) also demonstrated scavenging properties towards the 2,2-diphenyl-1-picryl-hvdrazvl (CDPPH) radical in TLC autographic and spectrophotometric assays.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800411
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  • 107
    Electronic Resource
    Electronic Resource
    Reformulating the Kinetic Approach of Column Chromatography for a Single Component (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1176-1182 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic model of column chromatography is revisited to explicitly show that this approach yields, when neglecting axial dispersion, a rather simple analytical expression depending only on two dimensionless parameters, namely a dimensionless kinetic retention parameter and a dimensionless time parameter. An expression for the time corresponding to the maximum of the peak is also proposed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800415
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  • 108
    Electronic Resource
    Electronic Resource
    Synthesis of Unnatural Lipohilic N-(9H-Fluoren-9-ylmethoxy)carbonyl-Substituted α-Amino Acids and Their Incorporation into Cyclic RGD-Peptides: A structure-activity studyDedicated to Peter Welzel on the occasion of his 60th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1280-1300 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The αv/β3 integrin is implicated in human tumor metastasis and angiogenesis. It has been shown that structures of the sequence cyclo(-Arg1-Gly2-Asp3-D-Phe4-Xaa5-) (I) and cyclo(-Arg1-Gly2-Asp3-Phe4-D-Xaa5-) (II) bind with high affinity and the latter with high selectivity to this receptor. The residues Xaa and D-Xaa accept a broad variety of amino acids. Here, we report on the synthesis, activities, and conformational analysis of cyclic Arg-Gly-Asp (RGD) peptides containing liophilic amino acids Xaa or D-Xaa in position 5. For I, these were (2S)-2-aminohexadecanoic acid (Ahd) and N′-hexadecylglycine (Hd-Gly) and in II, D-Ahd and Hd-Gly, and, for control purposes, Ahd were incorporated (Fig. 1). The enantiomerically pure a-amino acids were obtained by non-enantioselective synthesis and subsequent enzymatic separation of isomers using acylase I (Scheme). Hd-Gly was prepared in a modified procedure according to Stewart from ethyl bromoacetate and hexadecylamine (Scheme). The synthesis and physicochemical properties of the corresponding (9H-fluoren-9-ylmethoxy)carbonyl (Fmoc) derivatives, compatible with solid-phase peptide synthesis, are described. Structure elucidation by NMR reveals that the lipid modification has no significant impact on the template structures when incorporated into them. For peptides I with Xaa = Ahd or Hd-Gly (1 or 2), a βII′/γ-turn-like arrangement with D-Phe in i+1 position of the β-turn is found. Peptides II with D-Xaa = D-Ahd or Hd-Gly (3 or 4) exhibit a βII′/γ-turn conformation with Gly in i+1 position of the β-turn, whereas II with Ahd instead of D-Xaa, i.e., lacking a D-amino acid in position 4 or 5 (5). adopts no defined conformation. However, in assays of receptor specificity employing human αvv/β3 integrin, the compounds exhibit IC50 values ranging from nanomolar to less than millimolar. These results indicate that although the arrangement of the pharmacophoric groups is preserved in the target compounds, the biological activity is highly dependent on spatial requirements of the lipid anchor in the receptor binding pocket. Obviously, only certain positions do not affect the binding.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800423
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  • 109
    Electronic Resource
    Electronic Resource
    Cyclic Heptapeptides Axinastatin 2, 3, and 4: Conformational analysis and evaluation of the biological potentialDedicated to Ernst Bayer on the occasion of his 70th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1338-1354 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational analysis of naturally occurring cytostatic cyclic heptapeptides axinastatin 2, 3, and 4 was carried out by two-dimensional NMR spectroscopy in combination with distance-geometry (DG) and molecular-dynamics (MD) calculations in explicit solvents. The synthesized secondary metabolites were examined in (D6)DMSO. Axinastatin 2 was also investigated in CD3OH. In all structures, Pro2 is in the i + 1 position of a βI turn and Pro6 occupies the i + 2 position of a βVIa turn about the cis amide bond between residue 5 and Pro6. In all peptides, a bifurcated H-bond occurs between residue 4 CO and the amide protons of residue 1 and 7. For axinastatin 2 and 3, an Asn Ig turn was found about Asn1 and Pro2. We compared these structures with conformations of cyclic heptapeptides obtained by X-ray and NMR studies. A β-bulge motif with two β turns and one bifurcated H-bond is found as the dominating backbone conformation of cyclic all-L-heptapeptides. Axinastatin 2, 3, and 4 can be characterized by six trans and one cis amide bond resulting in a β/βVI(a)-turn motif, a conformation found for many cyclic heptapeptides. Detailed biological tests of the synthetic compounds in different human cancer cell lines indicates these axinastatins to be inactive or of low activity.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800503
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  • 110
    Electronic Resource
    Electronic Resource
    Synthesis via a Carbohydrate-Derived Münchnone of Pyrrolopyridines (Indolizines) and imidazopyridines, and their evaluation as inhibitors of β-D-glucosidasesDedicated to Oscar Jeger on the occasion of his 80th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1443-1456 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of activating agents, the N-acylglycine 8 reacts with electrophilic alkynes via the münchnone9 to the pyrrolopyridines (= indolizines) 10, 18, and 19 (Scheme 1 ), Depending on the nature of the activating agent and the reaction temperature, the formation of the pyrroles was accompanied by partial epimerization to the manna-configurated epimers 16 and 17. The gluco-configurated pyrrolopyridine 10 was deprotected to 12. Silylation of 12, followed by reduction and desilylation, gave the hexol 15. Cycloaddition of 9 to 4-toluenesulfonyl cyanide yielded 53% of the imidazole 23, while cycloaddition to phenyl cyanate gave the phenoxyimidazole 28 in low yields only (Scheme 2). As expected, the deprotected pyrroles 12, 15, 20, and 21 are weak inhibitors of retaining β-glucosidases, while the deprotected imidazole 24 derived from 23 proved a good inhibitor of sweet-almond β-glucosidases and a powerful inhibitor of Caldocellum saccharolyticum β-glucosidase.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800509
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  • 111
    Electronic Resource
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    Introduction of Amino Alcohols in the Ring-Opening Reaction of 3-bromo-2,5-dimethylthiophene 1,1-dioxide. A short diastereoselective synthesis of substituted ‘tetrahydrobenzo[a]pyrrolizidines’ (= octahydro-1H-pyrrolo[2,1-a]isoindoles) using L-prolinolDedicated to Prof. Dr. h. c. Dieter Seebach on the occasion of his 60th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1483-1493 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrahydrobenzo[a]pyrrolizidines (= octahydro-1H-pyrrolo[2,1-a]isoindoles) and tetrahydrobenzo[a]indo-lizidines, (= decahydropyrido[2,1-a]isoindoles) were prepared stereoselectively in four steps through an amineinduced ring-opening of 3-bromo-2,5-dimethylthiophene 1,1-dioxide (1) with L-prolinol (9), piperidine-2-methanol (10), and piperidine-2-ethanol (11), yielding the dienes (2S)-1-[(2E,4Z)-4-bromohexa-2,4-dienyl]pyrrolidine-2-methanol (12), 1-[(2E,4Z)-4-bromohexa-2,4-dienyl]piperidine-2-methanol (13), and 1-[(2E,4Z)-4-bromo-hexa-2,4-dienyl]piperidine-2-ethanol (14; Scheme2), which, after conversion into their α,β-unsaturated esters, cyclized in a TiCl4-catalyzed intramolecular Diets-Alder reaction (Scheme3). A discussion on the mechanism of the ring opening reaction including semiempirical and ab initio calculations is also presented.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800512
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  • 112
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    X-Ray Structure Analyses of Alkyl-Substituted N-Acryloyl- and N-CrotonoyltoluenesultamsDerived from saccharine (= 1,2-benzoisothiazol-3(2H)-one, 1,1-dioxide)Dedicated to the memory of Professor Wolfgang Oppolzer (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1607-1612 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The X-ray crystal-structure analyses of two N-enoyl-toluenesultam derivatives 1 are reported. The structural differences with their bornanesultam analogues 2 as well as stereochemical aspects with respect to their [4 + 2] and [3 + 2] cycloadditions are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800518
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  • 113
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    Metal Complexes with Macrocyclic Ligands. Part XXXVIIIPart XXXVII: [1].. Steric effects in the copper(II) and nickel(II) complexes with tetra-N-alkylated 1,4,8,11-tetraazacyclotetradecanes (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 505-513 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of tetra-N-alkylated 1,4,8,11-tetraazacyclotetradecanes have been synthesized and their complexation potential towards Ni2+ and Cu2+ studied. In the case of sterically demanding alkyl substituents, such as i-Pr, PhCH2, or 2-MeC6H4CH2, no metal complexes are formed, whereas for substituents such as Me, Et, and Pr, the metal ion is incorporated into the macrocycle. The spectroscopic properties of the Ni2+ and Cu2+ complexes in aqueous solution indicate that, depending on the sterical hindrance of the N-substituents, the complexes are either square planar or pentacoordinated. All these Ni2+ and Cu2+ complexes react with N3- to give ternary species, the stability of which have been determined by spectrophotometric titrations. The tendency to bind N3- decreases with increasing steric hindrance of the alkyl substituents. The X-ray studies of the Ni2+ complex with the macrocycle 11, substituted by two Me and two Pr groups, and that of the Cu2+ complex with the tetraethyl derivative 8 show that in the solid state, the metal ions exhibit square planar coordination with a small distortion towards tetrahedral geometry.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19950780220
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  • 114
    Electronic Resource
    Electronic Resource
    Masthead (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995) 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19950780301
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  • 115
    Electronic Resource
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    Synthesis of Galactose- and N-Acetylglucosamine-Derived Tetrazoles and their evaluation as β-glycosidase inhibitors (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 514-532 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compounds 6 and 7 have been prepared from the known 2,3-di-O-benzyl-4,6-O-benzylidene-D-galactose (18) and N2-acetyl-tri-O-benzyl-D-glucosamine oxime (29) in eight and six steps, respectively. The azidonitrile leading to the benzylated galacto-tetrazole 16 was prepared from 14 and cyclized under the conditions of its formation (Scheme 1). The alcohol 13 was obtained by oxidation of 10 followed by reduction. Better yields and diastereoselectivities were realized, when the benzylidene-protected D-galacto-alcohol 20 was subjected to oxido-reduction, yielding the L-altro-alcohol 22 via the ketone 21 (Scheme 2). Treatment of the corresponding tosylate 24 with NaN3 yielded the tetrazole 25, which was deprotected to 6. The tetrabenzyl ether 16 (from 14, or from 25 via 27) was reduced to 28 and deprotected to give the known deoxygalactostain 8 (Scheme 2). Oxidation of the hydroxynitrile 30, derived from 29, followed by reduction of 32 yielded mostly the L-ido-hydroxynitrile (Scheme 3), which was tosylated and treated with NaN3 to give the tetrazole 35a and its manno-isomer 36a, while Al(N3)3 yielded (E)- and (Z)-38 (Scheme 4). The intermediate azide 39 was isolated besides 40 when NH4N3/DMF was used; thermolysis of 39 gave mostly 35a, which was deprotected to 7, besides some elimination product 41. Both 6 and 7 are stable in the pH range 1-10; at pH 12, 6 is unaffected but, 7 shows some epimerization to the manno-configurated isomer 43. The tetrazole 6 is a competitive inhibitor of the β-galactosidases from E. coli (K1 = 1 μM, pH 6.8) and bovine liver (K1 = 0.8 μM, pH 7.0); the N-acetyl-β-D-glucosaminidase from bovine kidney is competitively inhibited by 7 (K1 ≊ 0.2 μM, pH 4.1).
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19950780221
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  • 116
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    Syntheses of the Enantiomers of γ-Cyclogeranic Acid, γ-Cyclocitral, and γ-Damascone: Enantioselective protonation of enolates (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 539-552 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (R)-and (S)-γ-cyclogeranic acid ((R)-and (S)-9, resp.) were obtained by resolution of the racemate, and their absolute configurations determined by chemical correlation. The γ-acids (R)-and (S)-9 were converted into (R)-and (S)-methyl γ-cyclogeranate ((R)-and (S)-6, resp.), and (R)-and (S)-γ-damascone ((R)-and (S)-5, resp.). A more direct entry to (R)-and (S)-9 consisted in the enantioselective protonation of a thiol ester enolate with (-)- or (γ)-N-isopropylephedrine((-)- or (γ)-20) and subsequent hydrolysis of the (R)-and (S)-S-phenyl γ-thiocyclogeranate ((R)- and (S)-24, resp.; 97% ee). The esters (R)- and (S)-24 were also used as precursors of (R)- and (S)-γ-damascone ((R)- and (S)-5, resp.). Alternatively, (S)-5 (75% ee) was obtained by enantioselective protonation of ketone enolate 29 with (-)-N-isopropylephedrine ((-)-20). Organoleptic evaluation demonstrated that the (S)-enantiomers of methyl γ-cyclogeranate and γ-damascone are markedly superior to their (R)-enantiomers.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19950780303
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  • 117
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    Microscopic Protonation/Deprotonation Equilibria of the Anti-Inflammatory Agent Piroxicam (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 553-562 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The microscopic ionization behavior of piroxicam was investigated using two different approaches, i.e., direct UV spectroscopy and an indirect analogue approach (deductive method). The best microscopic pKa values (pKa12 = 4.60, pKa21 = 5.40, pKa22 = 2.72, and pKa11 = 1.92) were obtained by the deductive method using as pKa22 the pKa of the enolic O-methylated piroxicam 2. The results show remarkable electrostatic effects in the protonation/deprotonation equilibria, a marked increase in the acidity of the enolic function (2.68 pKa units) being caused by the pyridinium group. The electronic structure of piroxicam was studied based on 1H-NMR chemical shifts at various ionization states, indicating an extended electron conjugation through the molecule. The partition measurements in octan-1-ol/H2O of zwitterionic compound 3 (the pyridyl N-methyl derivative of piroxicam (1)) suggest that the two opposite charges in zwitterionic piroxicam are indeed in a close intramolecular proximity.
    Additional Material: 3 Ill.
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    Oligosaccharides related to tumor-associate antigens. Part 3Part 2: [1].. Synthesis of the propyl glycosides of the trisaccharide β-D-Galp-(1→3)-β-D-GalpNAc-(1→3)-α-D-Galp and of the Tetrasaccharide α-L-Fucp-(1→2)-β-D-Galp-(1→3)-β-D-GalpNAc-(1→3)-α-D-Galp, components of a tumor antigen recognized by the antibody MBr1 (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 533-538 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the trisaccharide β-D-Galp-(1→3)-β-D-GalpNAc-(1→3)-α-D-Galp-1-OPr (2) and of the tetrasaccharide α-L-Fucp-(1→2)-β-D-GalpNAc-(1→3)-β-D-Galp-1-OPr (3), starting from the disaccharidic dihydrooxazole donor 5, is described. Glycosylation of 5 with 6 in the presence of Me3SiOTf gave the trisaccharide 7 which was deprotected with standard methods to give, via 8, compound 2 (Scheme 1). Alternatively, protection of 8 as the 4′,6′-O-benzylidene derivative 9 followed by glycosylation with 10 and by standard deprotection afforded the tetrasaccharide 3 (Scheme 2). Biological testing showed that trisaccharide 2 is unable to inhibit the binding of the monoclonal antibody MBr1 to the target tumor cells MCF7, while tetrasaccharide 3 inhibits the binding in ca. 7-fold extent with respect to the previously tested trisaccharide α-L-Fucp-(1→2)-β-D-Galp-(1→3)-β-D-GalpNAc-1-OPr. These results indicate that the galactose corresponding to the unit D of compound 1 plays an important role in defining the MBr1-recognized epitope and confirm the essential role of fucose for MAb recognition.
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    Structure and Dynamics of Hydrogen Chelates. Part 1. NMR-spectroscopic studies in the quinazoline-2-acetonitrile series (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 236-250 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To get informations on both the structure and dynamics of hydrogen chelates 1 of heteroaromatic systems, a great variety of quinazoline-2-acetonitrile chelates were synthesized (see 2-4). Similarly to the situation of the corresponding H-chelates in the pyrimidine-2-acetonitrile series, the investigation of these new derivatives 2-4 by NMR spectroscopic methods (DNMR, COSY, NOESY, ROESY, EXSY, HMQC, HMBC) confirms the presence of an equilibrium of the two possible H-chelate structures (two ‘rotamers’ I and II, i.e., (E)/(Z) isomers; see Scheme). The corresponding equilibria I ⇌ II were determined by complete 1H-NMR signal assignment at low temperatures (after freezing the rotational processes). In addition, the tautomer equilibria A ⇌ B (relative energies of the two minima of the nonsymmetrical double-well potential) for both ‘rotamers’ are ascertained by H,H and C,H couplings. The results are an important basis for the interpretation of both the UV/VIS absorptions and the dependence of fluorescence and fluorescence quantum yields on temperature.
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    Stereoselective Reactions of Phthalimido-Substituted Radicals Derived from (±)-Threonine: A comparison with reactions of N-phthaloyliminium ions (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 268-284 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoselective reactions of phthalimido-substituted radicals derived from (±)-threonine with different radical traps are reported (Scheme 3, Table 1). A strong influence of the nature of the radical trap on the stereoselectivity was noticed. Small nucleophilic radical traps gave preferentially the syn products. The observed selectivities are explained with the A1,3 strain model and depend on steric and electronic effects (Fig. 2). Reactions with electrophilic radical traps such as diphenyl diselenide gave the anti diastereoisomers with moderate stereocontrol, presumably due to stereoelectronic effects. The same stereochemical outcome, i.e., preferential formation of the anti products, was observed for the reactions of the related N-phthaloyliminium ion (Scheme 5, Table 2). The stereochemistry of the ionic reaction is rationalized by a Felkin-Anh model (Fig. 3).
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    Cyclopalladation of 1,1′-Azonaphthalene (= Di(naphthalen-1-yl)diazene): Isolation and characterization of two isomeric complexes (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 307-316 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclopalladation of 1,1′-azonaphthalene (= di(naphthalen-1-yl)diazene; 2) with bis(hexafluoroacetyl-acetonato)palladium(II) (3; [Pd(hfa)2]) yields the ortho-palladated complex (1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O′)[1-(naphthalen-1-ylazo-κN2)naphthalen-2-yl-κC2]palladium(II) (4) as well as the peri-palladated complex (1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O′)[8-(naphthalen-1-ylazo-κN2)naphthalen-1-yl-κC1]-palladium(II) (5); their structures were corroborated by X-ray analyses. The formation of the novel peri-metallated product 5 containing a six-membered palladacycle strongly depends upon the reaction conditions.
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    The Photoisomerization Behavior of the (4-Hydroxycinnamoyl)-spermidines (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 342-352 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photoisomerization behavior of three mono[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 1, 2, and 3, and three bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 4, 5, and 6, are investigated. The synthetic product (E)-1 could be almost quantitatively (〉 96%) converted into its isomer (Z)-1 under UV light irradiation. In the cases of (E)-2 and (E)-3, a mixture of (E)/(Z) ca. 1:2 was obtained, when the same conditions were applied. The comparison of their UV spectra provides the possible explanation for these different behaviors. Furthermore, it was noticed that the (Z) → (E) isomerization of the C=C bond took place during the purification by reverse-phase high-performance liquid chromatography (RP-HPLC), and the (E)/(Z)-mixture is thus inseparable. The same feature could be observed during the isolation of the (Z,Z)-N,N′-bis[3-(4-hydroxyphenyl)prop-2-enoyl]-spermidines, (Z,Z)-4, (Z,Z)-5, and (Z,Z)-6. Nevertheless, the fractions of (Z,Z)-5 and (Z,Z)-6 were in almost pure state collected, and their 1-NMR spectra are presented.
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    Boophiline, an Antimicrobial Sterol Amide from the cattle tick boophilus microplus (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 2066-2072 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Boophiline (1), a new sterol amide was isolated from the cattle tick Boophilus microplus (Ixodidae). The structure was assigned as N-[3-(sulfooxy)-25ξcholest-5-en-26-oyl]-L-isoleucine by detailed 2D NMR investigations in conjunction with FAB mass spectrometry and acidic hydrolyses. Complete assignment of the diastereotopic methylene protons of the ring system could be deduced from the NMR data. In agar dilution assays, 1 exhibited antifungal properties against Cladosporium cucumerinum and antibacterial activity against Bacillus subtilis and Escherichia coli.
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    Comparative Study of the Cope rearrangement of hexa-1,5-diene and barbaralane (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 2112-2123 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The classical rules for Cope rearrangements predict a transition state with chair form to be favored over the boat form. On the other hand, bridged homotropylidenes, which allow only a boat-form transition state by steric reasons, have extremely low barriers. A controversy about the correct pathway and the different possible intermediates and transition states of the reaction has gone on for years. In this work, the hypersurfaces of barbaralane, in comparison with the boat- and chair-form of hexa-1,5-diene, are computed by the ab inito CASSCF (6,6)/6-31G** method starting with UMP2/6-31G** natural orbitals (NO's). All three hypersurfaces show characteristic features, and, moreover differ from each other. A hitherto undiscussed intermediate, bicyclo[2.2.0]hexane, was localized on the boat-hexa-1,5-diene pathway. So it is noteworthy that our transition state for the boat-hexa-1,5-diene does not correspond to the transition states found by other authors for this conformation. The computed enthalpies of activation of boat- and chair-hexa-1,5-diene, and barbaralane are in good agreement with the experimental data.
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    Novel Leptomycins from a Streptomyces strain A92-308902: Inhibitors of the Nucleo-cytoplasmic translocation of the HIV-1 regulatory protein Rev (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 2157-2167 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As one of the regulatory gene products in the HIV-1 genome, Rev protein must be translocated from the nucleus to the cytoplasm to exert its function. Therefore, inhibition of Rev protein translocation could be a useful target for HIV therapy. An extract from the Streptomyces strain A92-308902 with very potent inhibitory activity was found in the course of a high throughput screening with a Rev translocation assay (RTA). Bioassay-guided fractionation with gel filtration, normal-phase and reversed-phase chromatography yielded six RTA-active metabolites belonging to the leptomycin family, the known leptomycin A (1), leptomycin B (2), kazusamycin B (3), and kazusamycin A (4). and the hitherto unknown dilactonmycin (5) and delactonmycin (6), together with an inactive cyclic hexadepsipeptide L-156,620 (7). The structures were established mainly by spectroscopic methods (UV, FT-IR, FAB-MS, 1H-NMR, 13C-NMR(JMOD), DQ-COSY, ROESY, HSQC, and HMBC). The configuration of all C=C bonds of 1-6 was unambiguously established by analysis of coupling constants and ROESY spectra. All isolated leptomycins 1-6 inhibit Rev translocation at nanomolar concentrations. Six derivatives (2a-c and 4a-c) of leptomycin B (2) and kazusamycin A (4) were also prepared and tested in the RTA for preliminary investigations on structure-activity relationships.
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    The Enantioselective Copolymerisation of allylbenzene, 1-allyl-4-(trifluoromethyl)benzene, and 1-allyl-4-methoxybenzene with carbon monoxide (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 2204-2214 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The olefins mentioned in the title were copolymerized with CO in the presence of palladium catalysts modified with dicyclohexyl{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}phosphine. Productivities up to 95 g/(gPd · h) were achieved. The obtained copolymers were recovered in the pure, regio- und stereoregular polyketone structures3. The isotactic poly[2-benzyl-1-oxopropane-1,3-diyl] (3a) and its analogues 3b, c were found to isomerize to the corresponding spirocyclic poly[3-(arylmethyl)tetrahydrofuran-2,2-5,5-tetrayl-2-oxy-2-methylene]s 4 in a suspension in CHC13, thus indicating that the spiroketal structure is thermodynamically the most stable for these copolymers. However, the atactic material did not undergo any structural transformation. These results show that regularity at the centers of chirality in the main chain is a prerequisite for the conversion of the polyketone to the spiroketal structure.
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    Synthesis, Structure, and Antimalarial Activity of Some Enantiomerically Pure, cis-fused cyclopenteno-1,2,4-trioxanes (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 647-662 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two pairs of enantiomerically pure cis-fused cyclopenteno-1,2,4-trioxanes (7, ent-7 and 8, ent-8) are prepared (Schemes 1-3). Their identities are established by dye-sensitized photo-oxygenation of ent-7 and 8, ent-8 to the allylichydroperxides, reduction to the corresponding alcohols, and conversion to the (1S)-camphanates (Scheme 4), the structures of which are determined by X-ray analysis. The dynamic properties of ent-7 are investigated by NMR spectroscopy and PM3 calculations. Evidence for an easily accessible twist-boat conformation is obtained. The in vitro and in vivo antimalarial activities of 7, ent-7,8, and ent-8 as well as those of the racemic mixtures are evaluated against Plasmodium falciparum, P. berghei, and P. yoelii. No correlation is observed between configuration and activity. Racemates and pure enantiomers have commensurate activities. The mode of action on the intraerythrocytic parasite is rationalized in terms of close docking by the twist-boat conformer of the trioxane on the surface of a molecule of heme, single-electron transfer to the O—O σ* orbital, and scission to the acetal radical which then irreversibly isomerizes to a C-centered radical, the ultimate lethal agent (Scheme 5).
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    Methyl and Phenylmethyl 2-Acetyl-3-{[2-(dimethylamino)-1-(methoxycarbonyl)ethenyl]amino}prop-2-enoate in the Synthesis of heterocyclic systems: Preparation of 3-amino-4H-pyrido-[1,2-a]pyrimidin-4-ones (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 2418-2425 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl 2-acetyl-3-{[2-(dimethylamino)-1-(methoxycarbonyl)ethenyl]amino}prop-2-enoate (4) and phenyl-methyl 2-acetyl-3-{[2-(dimethylamino)-1(methoxycarbonyl)ethenyl]amino}prop-2-enoate (5) were prepared in three steps from the corresponding acetoacetic esters, and used as reagents for the preparation of N3-protected 3-amino-4H-pyrido[1,2-a]pyrimidin-4-ones 10-12, 5H-thiazolo[3,2-a]pyrimidin-5-one 13, 4H-pyrido[1,2-a]-pyridin-4-one 19 and 2H-1-benzopyran-2-ones 20-23. Free 3-amino-4H-pyrido[1,2-a]pyrimidin-4-ones 24-26 were prepared from 10-12 by removal of the 2-(methoxycarbonyl)-3-oxobut-1-enyl or 3-oxo-2-[(phenyl-methoxy)carbonyl]but-1-envl as N-protecting group by various methods.
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    New Cyclophanes as Initiator Cores for the Construction of Dendritic Receptors: Host-guest complexation in aqueous solutions and structures of solid-state inclusion compounds (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 2368-2390 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclophanes 3 and 4 were prepared as initiator cores for the construction of dendrophanes (dendritic cydophanes) 1 and 2, respectively, which mimic recognition sites buried in globular proteins. The tetra-oxy[6.1.6.1]paracyclophane 3 was prepared by a short three-step route (Scheme 1) and possesses a cavity binding site shaped by two diphenylmethane units suitable for the inclusion of flat aromatic substrates such as benzene and naphthalene derivatives as was shown by 1H-NMR binding titrations in basic D2O phosphate buffer (Table 1). The larger cyclophane 4, shaped by two wider naphthyl(phenyl)methane spacers, was prepared in a longer, ten-step synthesis (Scheme 2) which included as a key intermediate the tetrabromocyclophane 5. 1H-NMR Binding studies in basic borate buffer in D2O/CD3OD demonstrated that 4 is an efficient steroid receptor. In a series of steroids (Table 1), complexation strength decreased with increasing substrate polarity and increasing number of polar substituents; in addition, electrostatic repulsion between carboxylate residues of host and guest also affected the binding affinity strongly. The conformationally flexible tetrabromocyclophane 5 displayed a pronounced tendency to form solid-state inclusion compounds of defined stoichiometry, which were analyzed by X-ray crystallography (Fig. 2). 1,2-Dichloroethane formed a cavity inclusion complex 5a with 1:1 stoichiometry, while in the 1:3 inclusion compound 5b with benzene, one guest is fully buried in the macrocyclic cavity and two others are positioned in channels between the Cyclophanes in the crystal lattice. In the 1:2 inclusion compound 5c, two toluene molecules penetrate with their aromatic rings the macrocyclic cavity from opposite sides in an antiparallel fashion. On the other hand, p-xylene (= 1,4-dimethylbenzene) in the 1:1 compound 5d is sandwiched between the cyclophane molecules with its two Me groups penetrating the cavities of the two macrocycles. In the 1:2 inclusion compound 5e with tetralin (= 1,2,3,4-tetrahydronaphthalene), both host and guest are statically disordered. The shape of the macrocycle in 5a-e depends strongly on the nature of the guest (Fig. 4). Characteristic for these compounds is the pronounced tendency of 5 to undergo regular stacking and to form channels for guest inclusion; these channels can infinitely extend across the macrocyclic cavities (Fig. 6) or in the crystal lattice between neighboring cyclophane stacks (Fig. 5). Also, the crystal lattice of 5c displays a remarkable zig-zag pattern of short Br…O contacts between neighboring macrocycles (Fig. 7).
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    An Efficient Synthesis of Optically Pure (R)- and (S)-2-(aminomethyl)alanine ((R)- and (S)-ama) and (R)- and (S)-2-(aminomethyl)leucine ((R)- and (S)-aml)Dedicated to Prof. M. Hesse on the occasion of his 60th birthday (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 703-714 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient synthesis of enantiomerically pure (R)- and (S)-2-(aminomethyl)alanine ((R)- and (S)-Ama) 1a and (R)- and (S)-2-(aminomethyl)leucine ((R)- and (S)-Aml) 1b is described (Schemes 1 and 2). Resolution of the racemic amino acids was achieved using L-phenylalanine cyclohexylamide (2) as chiral auxiliary. The free amino acids 1a, b were converted to the Nα-Boc,Nγ-Z-protected derivatives 11a, b (Scheme 3) ready for incorporation into peptides. Based on the three crystal structures of the diastereoisomeric peptides 8a, 8b, and 9b, the absolute configurations in both series were determined. β-Turn type-I geometries were observed for structures 8b and 9b, whereas 8a crystallized in an extended backbone conformation.
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    Determination of the Absolute Configuration of a Series of Halogenated Furanones from the marine alga delisea pulchra (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 758-764 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute configuration of a series of naturally occurring and semi-synthetic halogenated furanones is proposed on the basis of chemical interconversions and X-ray and CD analyses. The CD analyses clearly reveal that the presence of the allylic O-atom has a strong influence in determining the sign and intensity of the low energy π→π* transition.
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    An Efficient Straightforward Synthesis of Benz[a]azulene (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 765-771 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benz[a]azulene (1) is synthesized in five steps (cf. Scheme 2) starting from commercially available 2-iodobenzyl alcohol (4) and tropylium tetrafluoroborate in an overall yield of 44%. The key step (cf. also Scheme 1) is the intramolecular Heck reaction of the 8-phenylsulfonyl-substituted heptafulvene 7, which leads in nearly quantitative yield directly to 10-(phenylsulfonyl)benz[a]azulene (8). The desulfonylation of 8 can be accomplished by Julia's method with Na2S2O4/NaHCO3 in DMF/H2O at 85-90°, thus leading to pure 1 in 78% yield. The phenylation of 8 with PhLi or PhCul at -78° in THF occurs regioselectively at C(9). Dehydrogenation of the formed dihydroazulenes with o-chloroanil in toluene at room temperature gives 9-phenyl-10-(phenylsulfonyl)-benz[a]azulene (9) in 70% yield (cf. Scheme 3), which, again, can be desulfonylated with Na2S2O4/NaHCO3 in DMF/H2O in good yields. The addition of PhLi to 1 in THF occurs at temperatures ≥ -25°. Ionic dehydrogenation (1. Ph3C+BF4-/MeCN; 2. Et3N) of the dihydro forms leads to 3, as the main product, and its positional isomers.
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    Oligosaccharide Analogues of Polysaccharides. Part 3. A new protecting group for alkynes: Orthogonally protected dialkynes (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 732-757 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dialkynes of the type 3 (Scheme 1) are regioselectively deprotected by treating them either with base in a protic solvent (→4), or- after exposing the OH group- by catalytic amounts of base in an aprotic solvent (→5 and 8). The Me3Si-protected 12 (Scheme 2) is inert to catalytic BuLi/THF which transformed 11 into 9, while K2CO3/MeOH transformed both 10 into 9, and 12 into 13, evidencing the requirement for a more hindered (hydroxypropyl)silyl substituent. C-Silylation of the carbanions derived from 17-19 (Scheme 3) with 15 led to 20-22, but only 22 was obtained in reasonable yields. The key intermediate 27 was, therefore, prepared by a retro-Brook rearrangement of 23, made by silylating the hydroxysulfide 16 with 15. The OH group of 27 was protected to yield the {[dimethyl(oxy)propyl]dimethylsilyl}acetylenes (DOPSA's) 21, 28, and 29. The orthogonally protected acetylenes 20-22, 28, and 29 were de-trimethylsilylated to the new monoprotected acetylene synthons 30-34. The scope of the orthogonal protection was checked by regioselective deprotection of the dialkynes 39-42 (Scheme 4), prepared by alkylation of 35 (→39), or by Pd0/CuI-catalyzed cross-coupling with 36-38 (→40-42). The cross-coupling depended upon the solvent and proceeded best in N,N,N′,N′ -teramethylethylenediamine (TMEDA). Main by-product was the dimer 43. On the one hand, K2CO3/MeOH removed the Me3Si group and transformed 39-42 into the monoprotected 44-47; catalytic BuLi/THF, on the other hand, transformed the alcohols 48-51, obtained by hydrolysis of 39-42, into the monoprotected dialkynes 52-55, all steps proceeding in high yields. Addition of the protected DOPSA groups to the lactones 56 (→57-59) and 62 (→63) (Schemes 5 and 6) gave the corresponding hemiketals. Reductive dehydroxylation of 57 and 58 failed; but similar treatment of 59 yielded the alcohol 61. Similarly, 63 was transformed into 64 which was protected as the tetrahydropyranyl (Thp) ether 65. In an optimized procedure, 62 was treated sequentially with lithiated 31, BuLi, and Me3SiCl (→66), followed by desilyloxylation to yield 60% of 67, which was protected as the Thp ether 68. Under basic, protic conditions, 68 yielded the monoprotected bisacetylene 69; under basic, aprotic conditions, 67 led to the monoprotected bisacetylene 70. These procedures are compatible with the butadiynediyl function. The butadiyne 73 was prepared by cross-coupling the alkyne 69 and the iodoalkyne 71 (obtained from 70, together with the triiodide 72) and either transformed to the monosilylated 76 or, via 77, to the monosilylated 78. Formation of the homodimers 74 and 75 was greatly reduced by optimizing the conditions of cross-coupling of alkynes.
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    Preparation and Absolute Configuration of (-)-(E)-α-trans-Bergamotenone (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 153-162 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, absolute configuration, and olfactive evaluation of (-)-(E)-α-trans-bergamotenone (= (-)-(1′S,6′R,E)-5-(2′,6′-dimethylbicyclo[3.1.1]hept-2′-en-6′-yl)pent-3-en-2-one; (-)-1), as well as its homologue (-)-19 are reperted. The previously arbitrarily attributed absolute configuration of 1 and of (-)-α-trans-bergamotene (= (-)-(1 S,6R)-2,6-dimethyl-6-(4-methylpent-3-enyl)bicyclo[3.1. 1]hept-2-ene; (-)-2), together with those of the structurally related aldehydes (-)-3a,b and alcohols (-)-4a,b, have been rigorously assigned.
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    New Synthesis and Chirality of (-)-4,4,4,4′,4′,4′-Hexafluorovaline (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 182-186 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (-)-(R)-4,4,4,4′,4′,4′-Hexafluorovaline hydrochloride ((R)-5) of 98% ee is prepared from β,β-bis(trifluoromethyl)acrylic acid (= benzyl 4,4,4-trifluoro-3-(trifluoromethyl)but-2-enoate; 1) in 4 steps with an overall yield of 9.6%. Key step is the separation of the TsOH salts of the diastereoisomers obtained by anti-Michael addition of (+)-(R)-1-phenylethylamine (2) to 1 (→ (R,R)-3). In contrast to the published (S)-chirality, the X-ray structure analysis of (R,S)-6 reveals, that (R)-chirality has to be assigned to the levorotatory (-)-4,4,4,4′,4′,4′-hexafluorovaline hydrochloride.
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    Tripodal Dodecadentate Ligands with Salicylamide and bipyridine binding sites for iron(II) and iron(III) coordination (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 207-218 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of tripodal dodecadentate ligands with salicylamide and bipyridine binding sites for iron(II) and iron(III) are presented.
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    N,N-Dialkylcarbamato Complexes of the d10 cations of copper, silver, and gold (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 219-230 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of CuO'Bu with CO2, and iPr2NH in the presence of PPh3, gives the dialkylcarbamato complex [Cu(O2CNiPr2)(PPh3)2] (1). The CO2/R2NH system (R = Me, Et) in an appropriate organic medium reacts with Ag2O giving the corresponding N,N-dialkylcarbamato complexes of analytical formula [Ag(C2CNR2)] (R = Me, 2; R = Et, 3). The methyl derivative 2 was characterized by X-ray diffraction methods. Crystal data of 2: for [Ag2(O2CNMe2)2], C6H12Ag2N2O4, mol. wt. 391.9; monoclinic, space group P21/c, a = 12.08(1), b = 3.797(2), c = 11.316(7) Å, β = 113.37(6)°, V = 476.3 Å3, Z = 2, Dc = 2.732 g cm-3; μ(MoKα) = 40.64 cm-1, F(000) = 376.0; R = 0.059, Rw = 0.067; g.o.f. 1.27. The structure consists of dinuclear [(Ag2OCNMe2)2] units with slightly distorted linearly two-coordinated Ag-atoms containing bridging carbamato groups to form a substantially planar eight-membered ring with an intra-annular Ag—Ag distance of 2.837(2) Å; the dinuclear units are further joined by Ag—O bonds to form an infinite array. Compound 3, which is presumably dinuclear, as suggested by cryoscopic measurements in benzene, undergoes a structural fission with PPh3, giving the mononuclear triphenylphosphine derivative [Ag(O2CNEt2)(PPh3)2] (4). The amine-catalyzed conversion of Ag2O into Ag2CO3, in the presence of the iPr2NH/CO2 system, is also reported. Cl-Exchange from [AuCl(PPh3)] with [Ag(O2CNEt2)] (3) gives the first N,N-dialkylcarbamato complex of gold, namely [Au(O2CNEt2)(PPh3)] (5), which crystallizes in the monoclinic system: C23H25AuNO2P · 0.5 C7H16, mol. wt. 625.5, space group P21/c; a = 13.212(5), b = 12.25(1), c = 16.795(6) Å, β = 109.09(2)°, V = 2568(2) Å3, Z = 4, Dc, = 1.618 g cm-3; μ(AgKα) = 31.40 cm-1, F(000) = 1236.0; R = 0.058; Rw = 0.064; g.o.f. 2.121. The compound contains two-coordinated Au-atom, namely to the P-atom and to the O-atom of the monodentate carbamato group, the P—Au—O bond angle being 174.7(3)°. The reaction with MeI showed these compounds to react predominantly at the carbamato O-atom giving the corresponding urethanes R2NCO2Me. Evidence was gathered for the transient coordination of CO to Ag in 3.
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    1,3-Oxathiole and Thiirane Derivatives from the Reactions of Azibenzil and α-diazo amides with thiocarbonyl compounds (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 285-302 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of α-diazo ketones 1a,b with 9H-fluorene-9-thione (2f) in THF at room temperature yielded the symmetrical 1,3-dithiolanes 7a,b, whereas 1b and 2,2,4,4-tetramethylcyclobutane-1,3-dithione (2d) in THF at 60° led to a mixture of two stereoisomeric 1,3-oxathiole derivatives cis- and trans-9a (Scheme 2). With 2-diazo-1,2-diphenylethanone (1c), thio ketones 2a-d as well as 1,3-thiazole-5(4H)-thione 2g reacted to give 1,3-oxathiole derivatives exclusively (Schemes 3 and 4). As the reactions with 1c were more sluggish than those with 1a,b, they were catalyzed either by the addition of LiClO4 or by Rh2(OAc)4. In the case of 2d in THF/LiClO4 at room temperature, a mixture of the monoadduct 4d and the stereoisomeric bis-adducts cis- and trans-9b was formed. Monoadduct 4d could be transformed to cis- and trans-9b by treatment with 1c in the presence of Rh2(OAc)4 (Scheme 4). Xanthione (2e) and 1c in THF at room temperature reacted only when catalyzed with Rh2(OAc)4, and, in contrast to the previous reactions, the benzoyl-substituted thiirane derivative 5a was the sole product (Scheme 4). Both types of reaction were observed with α-diazo amides 1d,e (Schemes 5-7). It is worth mentioning that formation of 1,3-oxathiole or thiirane is not only dependent on the type of the carbonyl compound 2 but also on the α-diazo amide. In the case of 1d and thioxocyclobutanone 2c in THF at room temperature, the primary cycloadduct 12 was the main product. Heating the mixture to 60°, 1,3-oxathiole 10d as well as the spirocyclic thiirane-carboxamide 11b were formed. Thiirane-carboxamides 11d-g were desulfurized with (Me2N)3P in THF at 60°, yielding the corresponding acrylamide derivatives (Scheme 7). All reactions are rationalized by a mechanism via initial formation of acyl-substituted thiocarbonyl ylides which undergo either a 1,5-dipolar electrocyclization to give 1,3-oxathiole derivatives or a 1,3-dipolar electrocyclization to yield thiiranes. Only in the case of the most reactive 9H-fluorene-9-thione (2f) is the thiocarbonyl ylide trapped by a second molecule of 2f to give 1,3-dithiolane derivatives by a 1,3-dipolar cycloaddition.
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    Masthead (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998) 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/hlca.19980810301
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    Synthesis of Chiral C2-Symmetric Binucleating Ligands (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 491-506 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of chiral enantiomerically pure C2-symmetric binucleating ligands is reported. Ligands of type 1-4, which consist of a phenolic or heterocyclic unit bridging two chiral dihydrooxazole rings. are readily accessible from chiral amino alcohols. Ligands 5a and 5b are composed of a cyclic urea or thiourea unit, respectively, and two 3,4-dihydro-2H-pyrrole rings containing a stereogenic center next to the N-atom. Compounds of this type are readily assembled from ethane-1,2-diamine and an imidothioic ester derived from pyroglutamic acid. These new ligands, which can coordinate two metals in close proximity to each other, are of interest regarding possible applications in asymmetric catalysis.
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    Stability and Lability of Dicopper Double-Stranded Helicates in Solution (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 548-557 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stability constants have been measured for a series of ligands based on a 2,2′-(pyridine-2,6-diyl)bis[1H-benzimidazole] unit which forms dinuclear double-stranded helical complexes with copper(I). Variation of different structural parameters confirms the importance of the coordinate bond, the stacking interactions, and the weakly bridging pyridine units observed by X-ray crystallography. The stabilities of the complexes depend strongly on the solvent, and in MeCN, which is a good solvent for copper(I), the complexes are less stable and assemble in a stepwise manner. The interconversion of the enantiomers may be followed by 1H-NMR and takes place on a millisecond time scale around room temperature. The trends in lability are similar to those found for the stability of the complexes.
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    7-Deazapurine Oligodeoxyribonucleotides: The effects of 7-deaza-8-methylguanine on dna structure and stability (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 570-583 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligodeoxyribonucleotides containing 7-deaza-2′-deoxy-8-methylguanosine (m8c7Gd; 2b) were prepared. For this purpose, the phosphonate 3a and the phosphoramidite 3b were synthesized and employed in solidphase oligodeoxyribonucleotide synthesis. The structures and the thermodynamic data of duplex formation of oligodeoxyribonucleotides containing 2b were investigated by temperature-dependent CD and UV spectra and compared with those containing 7-deaza-2′-deoxy-7-methylguanosine (m7c7Gd) or 7-deaza-2′-deoxy-guanosine (c7Gd; 2a). In general, compound 2b reduces the duplex stability. In case of the sequence d(m8c7G-C)4 (18), the B → Z transition was facilitated by the incorporation of 2b. Moreover, a single 7-deaza-8-methylguanine residue present in an oligodeoxyribonucleotide tract of guanine residues destabilizes the dG quadruplex significantly. This destabilization is more pronounced than in the case of 7-deazaguanine or 7-deaza-7-methyl-guanine.
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    Mitteilungen (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 913-913 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19960790330
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    β-Peptides: Synthesis by Arndt-Eistert homologation with concomitant peptide coupling. Structure determination by NMR and CD spectroscopy and by X-ray crystallography. Helical secondary structure of a β-hexapeptide in solution and its stability towards pepsin (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 913-941 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The β-hexapeptide (H-β-HVal-β-HAla-β-HLeu)2-OH (2) was prepared from the component L-β-amino acids by conventional peptide synthesis, including fragment coupling. A cyclo-β-tri- and a cyclo-β-hexapeptide were also prepared. The β-amino acids were obtained from α-amino acids by Arndt-Eistert homologation. All reactions leading to the β-peptides occur smoothly and in high yields. The β-peptides were characterized by their CD and NMR spectra (COSY, ROESY, TOCSY, and NOE-restricted modelling), and by an X-ray crystal-structure analysis. β-Sheet-type structures (in the solid state) and a compact, left-handed or (M) 31 helix of 5-Å pitch (in solution) were discovered. Comparison with the analogous secondary structures of α-peptides shows fundamental differences, the most surprising one at this point being the greater stability of β-peptide helices. There are structural relationships of β-peptides with oligomers of β-hydroxyalkanoic acids, and dissimilarities between the two classes of compounds are a demonstration of the power of H-bonding. The β-hexapeptide 2 is stable to cleavage by pepsin at pH 2 in H2O for at least 60 h at 37°, while the corresponding α-peptide H-(Val-Ala-Leu)2-OH is cleaved instantaneously under these conditions. The implication of the described results are discussed.
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    Novel Cholic-Acid-Type Sterones of Deltocyathus magnificus, a deep-water scleractinian coral from the Loyalty Islands, SW Pacific (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 982-988 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cholic-acid-type 3-keto steroids 1-8, all isolated from Deltocyathus magnificus (2-8 after CH2N2 treatment), are the first secondary metabolites obtained from a deep-water scleractinian. Steroids 1-3, 5, and 7 are new, their main structural oddities being loss of C(24) (see 5) or hydroxylation in the side chain (see 3 and 7). Steroids 4, 6, and 8, from the same coral, were previously known from other marine organisms.
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    Acid-Catalysed Backbone Rearrangement of cholesta-6,8(14)-dienes (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 989-998 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rearrangement of 5α- and 5β-cholesta-6,8(14)-dienes (13a and 13b, resp.) in the presence of anhydrous toluene-4-sulfonic acid in acetic acid leads to 5α- and 5β-12(13 → 14)-abeo-cholesta-8,13(17)-dienes (15a and 15b, resp.) via 5α- and 5β-cholesta-8,14-dienes (14a and 14b, resp.), respectively. Epimerization at C(20) of the spirosteradienes 15a and 15b occurs with increasing reaction time. Molecular-mechanics calculation of the relative stabilities of these compounds and of congeners thereof is in agreement with the observed reaction pathway.
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    Absolute rate Constants for the Addition of Malonyl Radicals to Alkenes in Solution (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 770-780 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants and their Arrhenius parameters are obtained for the addition of a cyclic malonyl radical derived from Meldrum's acid to 20 mono- or 1,1-disubstituted alkenes in (±)-propylene oxide and for the addition of the open-chain di(tert-butyl)malonyl radical to six mono- or 1,1-disubstituted alkenes in 1,1,2-trichloro-1,2,2-trifluoroethane by time-resolved electron spin resonance spectroscopy. At room temperature, the radicals add at the unsubstituted C-atoms with rate constants ranging from 1.1. 105 M-1S-1 (acrolein) to 2.4. 106 M-1S-1 (1,1-diphenylethene). The frequency factors are in the narrow ranges of log (A/M-1S-1) = 8.7 ± 0.1 for the cyclic and log (A/M-1S-1) = 8.2 ± 0.2 for the open-chain malonyl species, whereas the activation energies vary from 12.9 kJ/mol (1,1-diphenylethene) to 21.7 kJ/mol (acrylonitrile). They correlate with the alkene ionization potentials and, more weakly, with the reaction enthalpy. No correlation was found between the activation energies and the alkene electron affinities. Hence, the results confirm and quantify the electrophilic nature of malonyl radicals in addition reactions.
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    Synthesis of the Spermidine Alkaloid (-)-(4R)-Dihydroisomyricoidine (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 1303-1318 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An asymmetric synthesis of (-)-(4R)-dihydroisomyricoidine (28), a 13-membered amino lactam of type A, was performed by a diastereoselective Michael addition between the spermidine derivative 3 and the commercially available optically active ethyl carboxylate 4, and the cyclization of the resulting ω-amino acid 7 using diethyl phosphorocyanidate ((EtO)2POCN), followed by a Wittig reaction to introduce the (Z)-side chain. Some side reactions are also discussed.
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    Asymmetric Synthesis of the Alkaloids mayfoline and N(1)-acetyl-N(1)-deoxymayfoline (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1085-1094 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The total syntheses of the spermidine alkaloids (-)-mayfoline (11) and (+)-N(1)-acetyl-N(1)-deoxymayfoline (12) are described. These macrocyclic lactams belong to the most interesting conjugates of the polyamine derivatives very commonly found in nature. The enantioselective syntheses were achieved through resolution of the methyl 3-amino-3-phenylpropanoate (2) by recrystallization of its (+)-L-tartrate salt. Construction of the 13-membered ring ensued through condensation, reductive ring expansion (internal bond cleavage), and finally a transamidation reaction involving a second ring expansion.
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    Electrochemical Behaviour and Antioxidant Activity of Some Natural Polyphenols (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1147-1158 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of natural polyphenols (chlorogenic acid (9), cordigol (11), cordigone (12), danthrone (1), 1,5-dihydroxy-3-methoxyxanthone (2), eriosematin (7), flemichin D (8), frutinone A (6), mangiferin (4), quercetin (5), 1,3,6,7-tetrahydroxyxanthone (3) and verbascoside (10)) were investigated for their redox properties using cyclic voltammetry. The antioxidant properties of these compounds were also examined in two models, namely lipid peroxidation in rat synaptosomes and AAPH-mediated oxidation of serum albumin. Compounds with a catechol group (9, 4, 5, 3 and 10) were oxidized below 0.4 V and inhibited lipid peroxidation with IC50 values between 2 and 8 μM. Compounds having one or more isolated phenolic groups and showing an oxidation potential between 0.45 and 0.8 V (11, 12 and 8) inhibited lipid peroxidation with IC50 between 7 and 9 μM, except 2 (0.45 V), danthrone (0.96 V) and eriosematin which showed no or modest antioxidant activity. Some of the investigated compounds also protected albumin from oxidation, but no structure-activity relationship was apparent, suggesting that other factors beside redox potential influence this activity.
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    Glycosylidene Carbenes. Part 23. Regioselective glycosidation of deoxy- and fluorodeoxy-myo-inositol derivativesDedicated to Edgar Heilbronner on the occasion of his 75th birthday (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1169-1191 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To demonstrate the relevance of the kinetic acidity of individual OH groups for the regioselectivity of glycosylation by glycosylidene carbenes, we compared the glycosylation by 1 of the known triol 2 with the glycosylation of the diol D-3 and the fluorodiol L-4. Deoxygenation with Bu3SnH of the phenoxythiocarbonyl derivative of 5 (Scheme 1) or the carbonothioate 6 gave the racemic alcohol (±)-7. The enantiomers were separated via the allophanates 9a and 9b, and desilylated to the deoxydiols D- and L-3, respectively. The assignment of their absolute configuration is based upon the CD spectra of the bis(4-bromobenzoates) D- and L-10. The (+)-(R)-1-phenylethylcarbamates 13a and 13b (Scheme 2) were prepared from the fluoroinositol (±)-11 via (±)-4 and the silyl ether (±)-12 and separated by chromatography. The absolute configuration of 13a was established by X-ray analysis. Decarbamoylation of 13a ( → L-12) and desilylation afforded the fluorodiol L-4. The H-bonds of D-3 and L-4 in chlorinated solvents and in dioxane were studied by IR and 1H-NMR spectroscopy (Fig. 2). In both diols, HO—C(2) forms an intramolecular, bifurcated H-bond. There is an intramolecular H-bond between HO—C(6) and F in solutions of L-4 in CH2Cl2, but not in 1,4-dioxane; the solubility of L-4 in CH2Cl2 is too low to permit a meaningful glycosidation in this solvent. Glycosidation of D-3 in dioxane by the carbene derived from 1 (Scheme 3) followed by acetylation gave predominantly the pseudodisaccharides 18/19 (38%), derived from glycosidation of the axial OH group besides the pseudodisaccharides 16/17 (13%) and the epoxides 20/21 (7%), derived from protonation of the carbene by the equatorial OH group. Similarly, the reaction of L-4 with 1 (Scheme 4) led to the pseudodisaccharides 28/29 (46%) and 26/27 (14%), derived from deprotonation of the axial and equatorial OH groups, respectively. Formation of the epoxides involved deprotonation of the intramolecularly H-bonded tautomer, followed by intramolecular alkylation, elimination, and substitution (Scheme 4). The regio- and diastereoselectivities of the glycosidation correlate with the H-bonds in the starting diols.
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    A Novel Asymmetric Benzoin Reaction Catalyzed by a Chiral Triazolium Salt. Preliminary communication (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1217-1221 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the chiral triazolium salt 1 as catalyst, a novel asymmetric variant of the benzoin reaction is reported. For the first time, the scope of the method is extended to a broader range of aromatic aldehydes 2, affording the acyloins 3a-h in yields of 22-72% and enantiomeric excesses up to 86%.
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    Erratum (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1239-1239 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/hlca.19960790429
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    Variation and SelectionDedicated to Professor Vladimir Prelog on the occasion of his 90th birthday (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1260-1278 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ninety years ago, chemical methods were used in solving biological problems. In our days, methods of evolutionary biology are going to be used in solving problems of synthetic chemistry.
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  • 155
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    Oligosaccharide Analogues of Polysaccharides. Part 8. Orthogonally Protected Cellobiose-Derived Dialkynes. A Convenient Method for the Regioselective Bromo- and Protodegermylation of Trimethylgermyl- and Trimethylsilyl-protected DialkynesDedicated to Vlado Prelog on the occasion of his 90th birthday (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1279-1294 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cellobiose-derived dialkynes 14 and 15 were prepared by glycosidation of the acceptor 9 with the thioglycosides 12(82%) and 13(85%), respectively. The acceptor 9 was prepared from the known alcohol 2 via the lactone 7 in five steps (48% overall), and the donors 12 and 13 were prepared from the alkynylated anhydroglucose derivative 10 (60% overall). Acetolytic debenzylation of 14 and 15 (→16 and 17, resp.) followed by deacylation of 16 yielded 60% of the cellobiose-derived dialkyne 18. Deacylation of 14 (→19), methoxymethylation (→20) and trimethylgermylation led to the orthogonally protected dialkyne 21 (69% overall). Protodesilylation of 21 with K2CO3/MeOH gave 22 (90%), while the Me3Ge group was selectively removed with CuBr (19 mol-%) in THF/MeOH to give 20 (95%). Treatment of 21 with aqueous HCl solution led to 19 (80%). Bromodegermylation of 21 (NBS/AgOOCCF3) led to a mixture of 23 (85%) and 24 (11%). Similar conditions using CuBr instead of AgOOCCF3 gave exclusively the bromoalkyne 23 (93%). The temperature dependence of the δ values of the OH resonances of 18 in (D6)DMSO evidence a strong intramolecular H-bond between C(5′)—O…HO—C(5).
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    Analogs of Cinchona Alkaloids Incorporating a 9,9′-Spirobifluorene MoietyDedicated to Professor Vladimir Prelog on the occasion of his 90th birthday (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1338-1360 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cinchona alkaloid analogs (+)- and (-)-5 with a quinuclidine-2-methanol residue attached to C(2) of a 9,9′-spirobifluorene moiety were prepared as a racemic mixture by reacting lithiated 2-bromo-9,9′-spirobifluorene 7 with (2-ethoxycarbonyl)quinuclidine (±)-6 to give ketone (±)-8, followed by diastereoselective reduction with diisobutylaluminum hydride (DIBAL-H). The absolute configuration at C(9) and C(8), i.e., at the methanol bridge and the adjacent quinuclidine C-atom, in the two enantiomers of 5 is identical to the configuration at the corresponding centers in (-)-quinine (1) and (+)-quinidine (2), respectively. For the optical resolution of (±)-5, a chiral stationary phase for HPLC was prepared by covalently bonding quinine via a thiol spacer to a silica-gel surface. The enantiomer separation was accomplished at an α value of 1.61 with (±)-5 being eluted last, in agreement with 1H-NMR studies in CDCl3 which showed that (+)-5 underwent a more stable host-guest association with quinine than (-)-5. 1H{1H} Nuclear Overhauser effect (NOE) difference spectroscopical analysis of the host-guest associations with quinine in CDCl3, combined with computer-model examinations, allowed the assignment of the absolute configurations as (+)-(8R,9S)-5 and (-)-(8S,9R)-5. A detailed conformational analysis displayed excellent agreement between the results of computational methods (Monte Carlo multiple minimum simulations, analyses of the total energy as a function of the flexible dihedral angles in the molecule) and 1H{1H}-NOE difference spectroscopical data. It was found that (-)-5 and (+)-5 differ significantly in their conformational preference from their natural counterparts quinine (1) and quinidine (2). Whereas the natural alkaloids prefer the ‘open’ conformation, with the quinuclidine N-atom pointing away from the quinoline ring, analog (±)-5 adopts preferentially (by ca. 4 kcal mol-1) a ‘closed’ conformation, in which the quinuclidine N-atom points into the cleft of the 9,9′-spirobifluorene moiety. Since the basic quinuclidine N-atom in the ‘closed’ conformation is sterically shielded from forming strong H-bonds, the new Cinchona alkaloid analogs form less stable host-guest associations via H-bonding than quinine or quinidine.
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    A New Approach to the Synthesis of Long-Chain Polypropionates Based on the Diels-Alder Monoadditions of 2,2′-Ethylidenebis[3,5-dimethylfuran]Part of the Ph.D. thesis of J.A., University of Lausanne, 1995. (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1393-1414 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acidic condensation of 2,4-dimethylfuran with acetaldehyde provided 2,2′-ethylidenebis[3,5-dimethylfuran] (7) which added 1 equiv. of methyl bromopropynoate to give a major adduct 8. Regio- and stereoselective hydroboration of the latter 7-oxanorbornadiene derivative followed by alcohol protection and methanolysis of its β-bromoacrylate moiety gave (1RS,2RS,4RS,5SR,6SR,1′RS)-methyl 4-[1′-(3″,5″-dimethylfuran-2″-yl)ethyl]-3,3-dimethoxy-6-exo-[(2-methoxy)ethoxy]-1,5-endo-dimethyl-7-oxabicyclo[2.2.1]heptane-2-endo-carboxylate (24) (Schemes 2 and 3). Reduction of 24 with LiAlH4, followed by H2O and MeOH elimination gave the 3-methyl-idene-7-oxanorbornan-2-one derivative 26 which underwent 7-oxa ring opening through a SN2′ type of reaction with Me2CuLi (Scheme 4). Stereoselective hydrogenation and ketone reduction provided (1RS, 2SR,3RS,4RS,5RS,6RS,1′SR)-1- [1″-(3 ″,5″-dimethylfuran-2″-yl)]-c-3-ethyl-c-5-[(2-methoxyethoxy)m e-c-ethyl-c-c-5-(2-methoxyethoxy)methoxy]-t-4,t-6-dimethyl-cyclohexane-r-1,c-2-diol (32), the oxidative cleavage of which with Pb(OAc)4 generated a 6-oxo-aldehyde 33 (Schemes 4 and 5). Chemoselective protection of 33 and chemo- and stereoselective reductions generated (2RS,3RS,4SR,5SR,6SR,7RS)-7-(3′,5″-dimethylfuran-2′-yl)-2-ethyl-6-hydroxy-4-[(2-methoxyethoxy)methoxy]-3,5-dimethyloct-1-yl pivaloate (36) and its 4-hydroxy 6-epimer 40 (12 and 13 steps, resp., from adduct 8; Scheme 5). Oxidation of the furan ring of 36 led to a (2RS,3SR,4RS,5SR,6RS,7RS)-7-ethyl-3,5,8-trihydroxy-2,4,6-trimethyl-octanoic acid derivative 44, a polypropionate fragment with six contiguous stereogenic centres (Scheme 6).
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    Isomerisierung von (all-E)-Cycloviolaxanthin Herstellung und Charakterisierung von (9Z)-und (13Z)-Cycloviolaxanthin (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1444-1450 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isomerization of (all-E)-Cycloviolaxanthin. Preparation and Characterization of (9Z)- and (13Z)-CycloviolaxanthinFrom (all-E)-cycloviolaxanthin (ex Capsicum annuum), (9Z)- and (13Z)-cycloviolaxanthin were prepared in a highly pure state. The configuration of both isomers was determined by means of UV/VIS, NMR, and CD spectroscopy.
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    Mitteilungen (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1518-1518 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19960790523
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  • 160
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    Intramolecular Vinyl Radical Cyclization Reactions of cyclohexadienes derived from sequential additions to (arene)(tricarbonyl)chromium complexes. Preliminary communicationDedicated to the memory of our late colleague Wolfgang Oppolzer (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1533-1536 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclohexa-1,3-dienes 7-10 with a 1,5,6-substitution pattern were prepared in a one-pot reaction sequence by sequential addition of MeLi and propargyl bromides to the tricarbonylchromium complex 1a. These products were subjected to radical cyclization procedures. Vinyl radical generation by Bu3Sn addition to the propargyl group in 7-10 was followed by regio- and diastereoselective intramolecular ring closure. Two different 5-exo-trig cyclizations are possible via different vinyl radical intermediates and cyclization to one or the other of the termini of the cyclohexadiene moiety. Internal alkynes reacted to yield exclusively the cis-fused hexahydroindene products 12-14, whereas the terminal alkyne yielded bicyclo[3.2.1]octenes 11 as sole products.
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    New Types of Potentially Antimalarial Agents: Epidioxy-substituted norditerpene and norsesterpenes from the marine sponge Diacarnus levii (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 1285-1292 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Natural free carboxylic acids from the hadromerid sponge Diacarnus levii (Kelly-Borges and Vacelet) were esterified to yield the new cyclic norditerpene peroxides ent-muqubilin benzyl ester (= (αR,3S,6R)-α,6-dimethyl-6-[(E)-4-methyl-6-(2,6,6-trimethyl-cyclohex-1-en-1-yl)hex-3-enyl]-1,2-dioxan-3-acetic acid benzyl ester; 6, diacarnoate B methyl ester(= (αS,3R,6R)-α,6-dimethyl-6-{2-(4aS,8aS)-3,4,4a,5,6,7,8,8a-octahydro-3-oxo-2,5,5,8a-tetramethylnaphthalen-1-yl)ethyl}-1,2-dioxan-3-acetic acid methyl ester; 9), and deoxydiacarnoate B benzyl ester (= (αS,3R,6R)-α,6-dimethyl-6-{2-[(4aS,8aS)-3,4,4a,5,6,7,8,8a-octahydro-2,5,5,8a-tetramethyl-1-naphthalenyl]ethyl}-1,2-dioxan-3-acetic acid benzyl ester; 10), which were isolated following extensive chromatography. The relative configuration of the peroxide/α-methylacetate moiety of 6, 9, and 10, was directly determined from their NMR spectra. The absolute configurations of the peroxide/α-methylacetate moiety was deduced from comparative 1H-NMR data of the (S)- and (R)-phenylglycine methyl ester derivatives 7 and 8 as well as 11/13 and 12/14, all obtained from a mixture of the precursors of 3, 6, and 10. The absolute configuration at the carbobicyclic moiety of enone 9 and of 10, is identical, as established by chemical interconversion, 9 and 10 belong to the normal labdane series according to empirical CD rules, applied either directly to 9 or to the parent (+)-sclareolide-derived enone 20. In contrast, molar rotation additivity rules suggest the ent-labdane configuration for 9 and 10. The epidioxides 1-3, 6, and 10 proved active in vitro against the malaria parasite Plasmodium falciparum; especially the previously isolated methyl 3-epinuapapuanoate (2) was active against a chloroquine-resistant strain, and this with a good security index.
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    3-Hydroxy-2-cyanoalk-2-enamides, and 2-Cyano-2-(tetrahydrofuran-2-ylidene)- and 2-Cyano-2-(tetrahydropyran-2-ylidene)acetamides: Synthesis, structure, and solvent-dependent (Z)/(E)-isomerismDedicated to Professor D. Seebach on the occasion of his 60th birthday (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 1319-1328 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Hydroxy-2-cyanoalk-2-enamides, and 2-cyano-2-(tetrahydrofuran-2-ylidene)- and 2-cyano-2-(tetrahydropyran-2-ylidene)acetamides with N-alkyl and N-aryl substituents have been synthesized in three steps from cyanoacetic acid. Their conformations were investigated by X-ray crystallography and 1H-NMR ROESY spectroscopy at room temperature. The enolic compounds 1-3 adopt an extended conformation stabilized by a strong intramolecular O—H … O=C bond both in the solid state and in (D6)DMSO solution. In contrast, the structure of the cyclic derivatives 5a,b-8a,b is solvent-dependent. In the solid state and in CDCl3 solution, the compounds adopt an extended conformation of type I or III, while, in (D6)DMSO solution, their structures undergo time-dependent (Z)/(E)-isomerization structures (of type II or IV). This observation is compatible with a dipolar transition state of rotation. The kinetics of the isomerization are controlled by the N-substituent, the N-(t-Bu) derivatives 7a and 7b having the highest barrier of rotation around the C=C bond. The whole body of experimental evidence together with the results of molecular-mechanics calculations with I-IV, indicate that, in DMSO, two (E)/(Z)-isomers with two conformations are present, and that they undergo interconversion at room temperature with four different constants. The very fast exchange rates kI,II and kIII,IV in the NMR time-scale might be responsible for the detection of only two isomers.
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    Monoterpene Dimers from Lisianthius seemannii (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 1393-1403 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new acylated dimeric secoiridoid glycoside, seemannoside A (2), has been isolated from the aerial parts of Lisianthius seemannii (GRISEB) O. KUNTZE (Gentianaceae). The structure was established by spectroscopic analysis (UV, MS, 1H- and 13C-NMR, and 2D-NMR experiments) and chemical reactions as (E-4′-O-p-coumaroyl)lisianthioside. The structure of the (Z)-isomer (seemannoside B, 3), also present in the plant, was confirmed by LC/UV/1H-NMR analysis. The active principle, 6, responsible for the antifungal activity of the apolar extract against Cladosporium cucumerinum, has been isolated. Its structure has been established by NMR spectroscopy and X-ray crystallographic analysis as a rare type of aglycone monoterpene dimer.
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    Asymmetric synthesis of pentono- and 6-deoxyhexono-δ-lactams via hetero-Diels-Alder reactions with nitroso dienophile (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 1417-1428 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric Diels-Alder reaction of the pentadienoic and hexadienoic acids 2a,b with the chiral chloronitroso derivative 3 gave the primary adducts 4a,b with good-to-excellent enantioselectivity. Subsequent as- or trans-dihydroxylation and hydrogenolytic cleavage of the N—O bond led to the 5-amino-5-deoxypentono-δ-lactams 13a, 14, 15a, and 16 in the D-ribose, L-arabinose, D-xylose, and L-lyxose series, respectively, and to the 5-amino-5,6-dideoxyhexono-δ-lactams 13b and 15b in the D-allose and D-glucose series, respectively.
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    The First Asymmetric Intramolecular Stetter Reaction. Preliminary Communication (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1899-1902 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first asymmetric intramolecular Stetter reaction is reported, using the chiral triazolium salt 1 as catalyst. Starting from the easily accessible 4-(2-formylphenoxy)but-2-enoates 2, this protocol opens up an enantioselective pathway to the benzo-annulated pyran-4-ones (chroman-4-ones) 3a-h with good yields and enantiomeric excesses of up to 74%.
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    URL: http://dx.doi.org/10.1002/hlca.19960790712
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    Reactions of 3-(Prop-2-enylidene)azetidin-2-ones with 4,5-Dihydro-3H-1,2,4-triazole-3,5-dionesDedicated to Prof. Gunther Seitz. Marburg. on the occasion of his 60th birthday (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1925-1929 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 3-(2-propenylidene)-β-lactams 1a-c react as semicyclic dienes with the dihydrotriazole-diones 2 in a stereoselective fashion leading to the cycloadducts 3. The 3′,3′-disubstituted derivative 4 gives no [4 + 2]-cycloaddition products but forms the adducts 5 and 6. Sterochemistry and reaction pathways are discussed.
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    Mechanistic Details of the Fe+-Mediated C—C and C—H Bond Activations in Propane: A Theoretical Investigation (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1939-1956 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantum-chemical calculations employing a density-functional theory/Hartree-Fock hybrid method (B3LYP) have been used to explore the mechanistic details of the C—C and C—H bond-activation processes in propane mediated by a bare Fe+ ion. While the theoretically predicted results are in complete accord with all available experimental data, they give rise to a different mechanistic picture than envisaged previously. In contrast to earlier speculation, the activation barriers for the initial insertion steps of Fe+ into a C—H or C—C bond are found to be significantly below the Fe+ + C3H8 channel. The rate-determining steps for both, the C—C and the C—H bond activation branches of the [FeC3H8]+ potential-energy surface rather occur late on the respective reaction coordinates and are connected with saddle points of concerted rearrangement processes. The C—C bond activation, which leads to the exothermic reductive elimination of methane, occurs via the C—C inserted species and not as a side channel originating from a C—H inserted ion, as assumed hitherto. For the C—H bond-activation processes, which finally results in the exothermic expulsion of molecular hydrogen, two energetically similar reaction channels for an [1,2]-elimination exist. The results clearly show, that an [1,3]-H2-elimination mechanism cannot compete with the [1,2]-elimination paths, in line with the experimental findings. Overall, a lower energy demand for the reductive elimination of methane compared to the loss of H2 is obtained, straightforwardly explaining the preference of the former process observed experimentally.
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    Masthead (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996) 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19960790801
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    Synthesis of 1,2,5-Thiadiazepine Derivatives by Ring Enlargement of 1,2-Thiazetidin-3-one 1,1-Dioxides with 3-Amino-2H-azirines (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 2067-2074 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At 0° in MeCN, 2,2-disubstituted 3-amino-2H-azirines 1 and 4,4-disubstituted 1,2-thiazetidin-3-one 1,1-dioxides 7 react smoothly to give 1,2,5-thiadiazepin-6-one 1,1-dioxides of type 8 (Scheme 2). The reaction mechanism of this regiospecific ring enlargement to seven-membered heterocycles follows previously described pathways. The structures of 7a and 8b were established by X-ray crystallography (see Figs. 1 and 2).
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    Biosynthesis of δ-Jasmin Lactone ( = (Z)-Dec-7-eno-5-lactone) and (Z,Z)-Dodeca-6,9-dieno-4-lactone in the Yeast Sporobolomyces odorus (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 2088-2099 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (all-Z)-(9,10,12,13,15,16-2H6)Octadeca-9,12,15-trienoic acid ( = α-linolenic acid; D6-4) was synthesized to investigate the biochemical formation of linolenic-acid-derived aroma compounds in cultures of the yeast Sporobolomyces odorus, using an established gas chromatographic/mass spectrometric (GC/MS) method. Three compounds were identified as labeled: (Z)-dec-7-eno-5-lactone (δ-jasmin lactone), (Z,Z)-dodeca-6,9-dieno-4-lactone, and (2E,4Z)-hepta-2,4-dienoic acid. Both lactones were biosynthesized mostly under conservation of the initial configuration from their corresponding oxygenated linolenic-acid intermediates. The application of (13S,9Z,11E,15Z)-13-hydroxy(9,10,12,13,15, 16-2H6)octadeca-9,11,15-trienoic acid (D6-7) as a OH-functionalized precursor of δ-jasmin lactone allowed to gain insight into the stereochemical course of the biosynthesis to both enantiomers of this lactone. In this experiment, 88.3% of the metabolized labeled precursor was transformed under retention of the original configuration of the (R)-enantiomer. This investigation is also a contribution to a better understanding of the C=C bond isomerization steps which took place during the β-oxidative degradation of the substrate.
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    5,5′-Bi-5H-cyclopenta[2,1-b;3,4-b′]dipridinylidene, a New Bridging Ligand for Metal Complexes. Preliminary Communication (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 2176-2179 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 5,5′-Bi-5H-cyclopenta[2,1-b;3,4-b′]dipyridinylidene(1) was synthesized in three steps from 9,10-phenanthroline and characterized by UV/VIS and NMR spectroscopy, mass spectrometry, and cyclic voltammetry. Its ability to act as a bridging ligand is demonstrated by the synthesis of the complexes [Ru(bpy)2(1)](PF6)2 (6) and [{Ru(bpy)2}2(1)](PF6)4 (7) (bpy = 2,2′-bipyridine).
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    Synthesis and Structure of Functionalized Cyclododecadiynes and -dienes (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 2164-2175 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclododecadiynes 3b-d, 8b-d, and 10b-c with functionalities in two propargylic positions, as well as the monofunctionalized diyne 13b have been prepared from simple open-chain building blocks. In the DMPU ( = N,N'-dimethylpropyleneurea)-assisted ring-closing alkylation of 1,7-diynes, the twelve-membered ring compounds have been prepared in yields of 16-55%. The preparation of the diene-diyne 15 and the cyclododeca-5,11-diyne-1,4-dione 18 are described.
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    Synthesis of Enantiomerically Pure Carbohydrate-Derived Annulated Cyclopentadienes and Ferrocenes (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 2201-2218 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclopentadienes 3a/b/c, 8b/c, 12a/b/d, and 16a/b/d were prepared as mixtures of regioisomers from the D-mannitol-derivatives 1,6,10, and 14 and transformed into the ferrocenes 17, 18, and 19 (73%; 38:17:45), 23, 24, and 25 (70%; 6:42 :52), 26 (31%), and 27 (27%), respectively. Deprotection of 17-19 with HCl/MeOH gave the H2O-soluble ferrocenes 20-22; chloromercuration and iodination of 17 via 29 led to the C2-symmetric diiodo-ferrocene 30. The mono(chloromercurio) derivative 28, obtained as a by-product, was also transformed into 29. The structure of the ferrocenes 18 and 19, and of the bis(chloromercurio)ferrocene 29 has been established by X-ray analysis. The starting cyclopentadienes 3 were obtained in 50% yield from 1 by dialkylation of CpNa, followed by thermolysis of the spiro-annulated 2. Similarly, dimesylate 6 (from 4) gave the spiro-annulated diene 7 and the annulated dienes 8 in about equal amounts; thermolysis transformed 7 into 8 (62%). The dienes 12 were prepared in 15% yield from the ditriflate 10 via 11, the dimesylate 9 proving insufficiently reactive, and the dienes 16 (49%) from 14 via 15.
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    Synthesis of Fused Triazoles as Probes for the Active Site of Retaining β-Glycosidases: From Which Direction Is the Glycoside Protonated? (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 2190-2200 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of the β-glycosidase inhibitors 1-7 and 10-13 suggests that protonation of O-C(1) (the glycosidic O-center) of the substrate by a carboxy group of the retaining β-glycosidases does not occur in the plane perpendicular to the ring of the glycon (β-side; ‘from the top’), but in the plane of the ring (‘from the side’). The triazoles 17 and 18 have been prepared in six steps from the L-xylofuranose 21. They possess a CH group instead of the N-center of the related tetrazoles 4 and 5, corresponding to the glycosidic O-atom, and a very similar structure, both in solution and in the solid state. Unlike the tetrazoles, however, which are good-to-medium inhibitors of retaining β-glycosidases, the triazoles do not inhibit the β-glycosidases from sweet almonds, snail, and bovine liver, and only slightly inhibit the β-glucosidase from Caldocellum saccharolyticum. This is in keeping with the proposed direction of protonation in the plane of the saccharide ring and with modelling studies, docking 4 into the active site of the white clover cyanogenic β-glucosidase and 6 into the E. coli β-galactosidase and the Lactococcus lactis 6-phospho-β-galactosidase.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19960790814
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    Double-Bond Shifts in [4n]Annulenes as a New Principle for Molecular Switches: First Results with Dimethyl Heptalene-1,2- and -4,5-dicarboxylatesDedicated to Vlado Prelog on the occasion of his 90th birthday (1996)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 2282-2315 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new concept for molecular switches, based on thermal or photochemical double-bond shifts (DBS) in [4n]annulenes such as heptalenes or cyclooctatetraenes, is introduced (cf. Scheme 2). Several heptalene-1,2- and -4,5-dicarboxylates (cf. Scheme 4) with (E)-styryl and Ph groups at C(5) and C(1), or C(4) and C(2), respectively, have been investigated. Several X-ray crystal-structure analyses (cf. Figs. 1-5) showed that the (E)-styryl group occupies in the crystals an almost perfect s-trans-conformation with respect to the C=C bond of the (E)-styryl moiety and the adjacent C=C bond of the heptalene core. Supplementary 1H-NOE measurements showed that the s-trans-conformations are also adopted in solution (cf. Schemes 6 and 9). Therefore, the DBS process in heptalenes (cf. Schemes 5 and 8) is always accompanied by a 180° torsion of the (E)-styryl group with respect to its adjacent C=C bond of the heptalene core. The UV/VIS spectra of the heptalene-1,2- and -4,5-dicarboxylates illustrated that it can indeed be differentiated between an ‘off-state’, which possesses no ‘through-conjugation’ of the π-donor substituent and the corresponding MeOCO group and an ‘on-state’ where this ‘through-conjugation’ is realized. The ‘through-conjugation’, i.e., conjugative interaction via the involved s-cis-butadiene substructure of the heptalene skeleton, is indicated by a strong enhancement of the intensities of the heptalene absorption bands I and II (cf. Tables 3-6). The most impressive examples are the heptalene-dicarboxylates 11a, representing the off-state, and 11b which stands for the on-state (cf. Fig.8).
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    Use of the Wolff Rearrangement of Diazo Ketones from Amino Acids as a synthetic method for the formation of oligonucleo-peptides: A novel approach to chimeric biomolecules (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1-13 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photolysis and Ag-benzoate-catalyzed decomposition of the diazo ketones 2 and 4 derived from Z-Ala-OH and Z-Ala-Ala-OH in the presence of oligonucleotide derivatives bearing at the 5′-terminus an NH2 instead of the OH group, or an aminohexyl phosphate group lead to Z-protected 3-aminobutanoyl and to Z-Ala-β-HAla derivatives, respectively (conjugates 12, 13, and 17-23, Schemes 3-5), In solution, this amide-forming acylation reaction could be realized only with oligomers containing up to 8 unprotected nucleotide building blocks (Schemes 3 and 4). With the analogous polymer-bound and protected oligonucleotide derivatives as amino nucleophiles, excellent yields were obtained with all chain lengths tested (up to 15mer Scheme 5), The products were purified by reversed-phase HPLC and characterized by MALDI-TOF mass spectrometry (Figs. 2-4, Table 2) and by capillary gel electrophoresis (Fig.2).
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    A Novel and Efficient Approach for the Combinatorial Synthesis of Structurally Diverse Pyrimidines on solid supportPresented in part at the ‘Random & Rational Conference’ in Princeton on September 16, 1996 (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 65-72 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe a versatile novel approach for the synthesis of 2, 4, 6-trisubstituted pyrimidines on solid support. Thus, polymer-boun J thiouronium salt 2 reacted in high yield in a cyclocondensation reaction with the acetylenic ketones 3 to form, after tert-butyl-ester cleavage, the polymer-bound carboxylic acids 4, which were cleaved by oxidation with 3-chloroperbenzoic acid and pyrrolidine to form the 2-pyrrolidinylpyrimidine-4-carboxylic acids 6a-c in high yields and purities without further purification (Scheme 1). Alternatively, acid 4a was subjected to an Ugi four-component condensation which gave the polymer-bound Ugi products 9a-e in good yields (Scheme 2). Multidirectional cleavage reaction of sulfone 8a with different nucleophiles resulted in the clean formation of pyrimidine-4-carboxamides 10-13 (Scheme 3). This strategy combines efficiently solid-phase chemistry with a multicomponent reaction and a multidirectional cleavage step to form highly diverse pyrimidines in a parallel array.
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    6-Azabicyclo[3.1.0]hex-30-en-2-ol Derivative, photochemically generated building blocks for bicyclic β-lactamsDedicated to Fabian Gerson to commemorate a long-standing collaboration (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 121-127 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compounds 4 are obtained by photolysis of simple N-alkylpyridinium salts in H2O or alcohol. On reaction with [Fe2(CO)9] in THF, 4 gives bicyclic tricarbonyliron complexes 13a-d, which on oxidative decomplexation with ceric ammonium nitrate afford cis-fused cyclopenteno-β-lactams 15a-d.
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    Models for the Active Center of Pterin-Containing Molybdenum Enzymes: Crystal structure of a molybdenum complex with sulfur and pterin ligands (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 103-110 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first crystal structure of a molybdenum complex 9 with a hydrogenated pterin and a sulfur ligand contributes to the discussion about the active center of molybdenum and tungsten enzymes containing a molybdopterin cofactor. Complex 9 was synthesized through a redox reaction of [MoVIO2 (LN-S2)] (8; LN-S2 = pyridine-2, 6-bis(methanethiolato)) with 5, 6, 7, 8-tetrahydropterin (7). 2 HCl (H4Ptr.2 HCl). The complex crystallizes, with a non-coordinating Cl-atom acting as a counterion, in the monoclinic space group C2/c (No. 15) with cell dimensions a = 22.900(5), b = 10.716(2), c = 17.551(4) Å, β = 120.36(3)°, and Z = 8. We interpret 9 as [MoIVO(LN-S2)(H+-q-H2Ptr)]Cl (q = quinonoid; H2Ptr = dihydropterin), i.e., a MoIV monooxo center coordinated by a pyridine-2, 6-bis(methanethiolato) ligand and a protonated dihydropterin. The spectroscopic properties of this new complex are comparable to those of other crystalline molybdenum complexes of hydrogenated pterins without additional S-coordination. The slightly H2O-soluble complex 9 reacts with the natural enzyme substrate DMSO very slowly, possibly due to the lack of easily dissociable ligands at the metal center.
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    Cyclo-β-peptides: Structure and tubular stacking of cyclic tetramers of 3-aminobutanoic acid as determined from powder diffraction dataDedicated to Professor Hans Paulsen on the occasion of his 75th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 173-182 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid-state structures of three stereoisomer, 1-3, of the cyclic tetramer of 3-aminobutanoic acid are presented. These cyclo-β-peptides were found to be highly insoluble materials, and it proved to be impossible to grow crystals of sufficient quality for X-ray single-crystal analysis. The samples of 1-3 were, however, suitable candidates for structure determination from powder diffraction data (Fig. 1), and the application of this method is described. All three isomers have been found to adopt tubular structures (Figs. 2-4) in a fashion similar to those already observed for certain cyclo-α-peptides. The stacks of 16-membered rings are held together by four nonlinear C=O…H—N H-bonds between pairs of molecules (Fig.5).
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    Partial Synthesis and Characterization of the Mono-and Diepoxides of β-Cryptoxanthin (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 221-229 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Cryptoxanthin (1) was acetylated and then epoxidized with monoperoxyphthalic acid. After hydrolysis, repeated chromatography, and crystallization, (3S,5R,6S)-5,6-epoxy-β-cryptoxanthin (3), (3S,5S,6R)-5,6-epoxy-β-cryptoxanthin (4), (3R,5′R,6′R)-5′,6′-epoxy-β-cryptoxanthin (5), (3S,5R,6S,5′R,6′S)-5,6:5′,6′-diepoxy-β-cryp-toxanthin (6), and (3S,5S,6R,5′S,6′R)-5,6:5′,6′-diepoxy-β-cryptoxanthin (7) were isolated as main products and characterized by their UV/VIS, CD, 1H- and 13C-NMR, and mass spectra. The comparison of the carotenoid isolated from yellow, tomato-shaped paprika (Capsicum annuum var. lycopersiciforme flavum) with 3-5 strongly supports the structure of 3 for the natural product.
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    Metal Complexes with Macrocyclic Ligands. Part XLIIIPart XLII [1]. Tetraazamacrocyclic nickel(II) and copper(II) complexes with aliphatic methylthio- and methoxy-substituted pendant chains (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 241-252 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 14-membered tetraazamacrocyclic Ni2+ and Cu2+ complexes of 4 (1, 4, 8-trimethyl-11-[(2-methylthio)ethyl]-1, 4, 8, 11-tetraazacyclotetradecane), 5. (1, 4-dimethyl-8, 11-bis[2-(methylthio)ethyl]-l, 4, 8, 11-tetraazacyclotetradecane), and 7 (1, 4, 8, ll-tetrakis[2-(methylthio)ethyl]-1, 4, 8, 11-tetraazacyclotetradecane), with pne, two, and four methylthio-substituted pendant chains, respectively, and the Ni2+ complex of 6 (1, 4-dimethyl-8, 11-bis (2-methoxyethyl)-1, 4, 8, 11-tetraazacyclotetradecane), with two methoxy-substituted pendant chains, were synthesized and their chemistry studied with regard to modelling F430. Solution spectra in H2O, MeCN, and DMF indicate participation of the side chain in metal coordination when the donor group is a thioether, whereas no coordination with the metal ion is observed with the ether group. Similarly the X-ray structures of the thioether-containing compounds [Ni(5)](ClO4)2, [Cu(5)](ClO4)2, and [Cu(7)](ClO4)2 show a coordination number of 5, whereas that of [Ni(6)](ClO4)2 with ether pendant chains, shows a coordination number of 4. Cyclic voltammetry of these complexes in MeCN reveals that Ni2+ is reversibly reduced to Ni+ between -0.64 and -0.77 V vs. SCE, the potential being influenced by the nature and number of the pendant chains. At more negative potentials, the thioether is cleaved, whereby a thiol is formed; the thiol is then oxidized at ca. + 0.8 V vs. SCE, when a glassy carbon electrode is used, or at ca. 0 V vs. SCE at a dropping Hg electrode. No cleavage of the ether bond in [Ni(6)](ClO4)2 is observed under similar conditions.
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    Masthead (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997) 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800201
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    Synthesis of Indole Derivatives by [2 + 2] Photocycloaddition of Indoline-2-thiones with alkenes and photodesulfurization of indoline-2-thiones (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 388-397 
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    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical synthesis of indole derivatives starting from the indoline-2-thiones 1 is described. Irradiation of indoline-2-thiones 1 in the presence of alkenes 3 gave 2-alkyl-3H-indoles 4-7 or 2-alkylindoles 8-22 through the ring cleavage of the intermediates, spirocyclic amino-thietanes, initially derived by [2 + 2] cycloaddition of the C=S bond of 1 and the C=C bond of 3. Irradiation of 1 in the presence of trialkylamines 26 gave desulfurization products 27-32 and unexpected 3-alkylindoles 33-40. N-Acylindoline-2-thiones 11-p yielded the deacylated products, indoline-2-thiones 1a-b, and ethyl esters 43 through γ-H abstraction by the excited thioamide S-atom when irradiated in CDC13/EtOH or benzene/EtOH. Oxygen analogues 2a-d also underwent intramolecular H abstraction to give the indolin-2-ones 2e-f and ethyl esters 43 in a similar way.
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    Isolation, Structure, and Biological Activities of Long-Chain Catechols of Plectranthus sylvestris (Labiatae) (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 436-448 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Antioxidant activity guided fractionation of extracts of the aerial parts of the title plant and HPLC separation yielded a series of oxygenated long-chain alkylcatechols. Their structures were inferred by spectroscopic methods and chemical transformations to be the novel 4-[(2S,4R,6S)-4-(acetyloxy)tetrahydro-6-pentyl-2H-pyran-2-yl]benzene-1,2diol (1a), 4-[(2S,4R6S)-tetrahydro-4-hydroxy-6-pentyl-2H-pyran-2-yl]benzene-1,2-diol (1b), 4-[(3S,5S)-5-(acetyloxy)-3-hydroxydecyl]benzene-1,2-diol (2a), 4-[(3S,5S)3-(acetyloxy)-5-hydroxydecyl]benzene-1,2-diol (2b), (3S,13Z)-1-(3,4-dihydroxyphenyl)-3-hydroxydocos-13-en-5-one (3a), (Z)-1-(3,4-dihydroxyphenyl)docos-13-en-5-one (4), besides the known l-(3,4-dihydroxyphenyl)icosan-5-one (5). The absolute configurations of the optically active compounds which are structurally related to the [n]-gingerols (6) and -diols (7) were established by the high-field 1H-NMR application of Mosher's method. All compounds are in vitro potent antioxidants, inhibiting the Fe2+-catalysed autoxidation of linoleic acid in the same order of magnitude as the commercial antioxidant 2,6-di(tert-butyl)-4-methylphenol (BHT). The dose-dependent inhibitory effects on soybean-lipoxygenase are in the μmol range, that of the most effective compound (3a) in the nmol range, hence being significantly more potent than the Known anti-inflammatory and analgesic drugs indomethacin and nordihydroguaiaretic acid.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800209
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  • 186
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    Synthesis and Structure of a Macrocyclic Europium Complex and its possible role as a catalyst for phosphodiester transesterification (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 487-494 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and X-ray crystal structure of a europium macrocyctic complex 1, an important catalyst used for the sequence-specific cleavage of RNA, is reported. The role of this metal complex in facilitating phosphate transesterification is discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800213
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  • 187
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    A Novel Approach towards 2,3,5-Trisubstituted Thiophenes via tandem Michael addition/intramolecular Knoevenagel condensation (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 531-537 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Starting from the easily available, highly functionalized acetylenic ketories 4a-i (Scheme 1), novel 2,3,5-trisubstituted thiophenes 1a-i (Scheme 2) were synthesized in good yields using a tandem Michael-addition/intramolecular Knoevenagel-condensation strategy, featuring Cs2CO3/MgSO4 (1:2) as an efficient base to effect the cyclization. Subsequent simple one-step transformations yielded 2,3-disubstituted thiophene-5-carbaidehydes 7a-c, carboxylic-acid derivatives 8, 9, and 11, and alcohol 10 (Scheme 3). These molecules constitute interesting novel thiophene-containing building blocks, useful for the preparation of low-molecular-weight compound libraries by combinatorial and parallel-chemistry techniques.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800217
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  • 188
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    Synthesis, Characterization, and Crystal Structure of Complexes of Lanthanide Picrates with N,N,N′,N′-tetraphenyl-3,6-dioxaoctanediamide (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 586-592 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lanthanide picrate complexes with the ligand N,N,N′,N′-tetraphenyl-3,6-dioxaactanediamide (tdd): [Ln(Pic)3(tdd)] (Ln = La, Nd, Eu, Tb, Er) have been prepared in a nonaqueous medium and characterized by elemental analysis, conductivity measurements, IR, and 1H-NMR spectra. The crystal structures of the complexes for Ln = Nd and Er were determined. The early lanthanide, NdIII, crystallizes as the nona-coordinate complex [Nd(Pic)3(tdd)]. 2 CH3CN in the monoclinic space group P21n with a = 11.384(2), b = 18.805(4), c = 27.526(5) Å, β = 99.41(1)°, V = 5832(2) Å3, and Dc = 1.58 gcm-3 for Z = 4. The structure was refined to R = 0.0505, based on 4772 observed Deflections. The late lanthanide, ErIII, forms an octa-coordinate complex [Er(Pic)3(tdd)]; crystals are triclinic, P1, with a = 12.449(2), b = 17.065(2), c = 26.243(4) Å, α = 72.12(1), β = 87.86(1), γ = 84.60(1)°, V = 5282(1) Å3, and Dc = 1.68 g cm-3 for Z, = 4. The structure was refined to R = 0.0469, based on 10666 observed reflections, The results reveal that tdd forms a ring-like structure with its four O-atoms, coordinating to the metal ions as multidentate ligand, together with one O-atom of the bidentate picrate. The structure of the complexes is greatly affected by the ionic radius due to participation of the picrates in coordination.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800221
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    Mitteilungen (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 622-622 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800225
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  • 190
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    Palladium-Catalysed Intramolecular Cyclisations of Olefinic Propargylic Carbonates and application to the diastereoselective synthesis of enantiomerically pure (-)-α-thujone (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 623-639 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intramolecular [Pd2(dba)3]/tri(2-furyl)phosphine-catalysed (dba = dibenzylideneacetone, PhCH=CHCOCH=CHPh) cyclisations of olefinic propargylic carbonates I provided alk-1-enyl-(3-aza)bicyclo[3.1.0]-hexanes VIII in good yields. A palladium cascade sequence I → II → III → IV → VII → VIII is proposed. Furthermore, chiral propargylic carbonates such as 23, 24 and 25 allowed diastereoselective formation of bicyclo[3.1.0]hexanes 29, 30 and 31, respectively. The first diastereoselective synthesis of the monoterpene, (-)-α-thujone 40 illustrates the potential of the method.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/hlca.19970800302
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  • 191
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    Rogioldiol A, a new obtusane diterpene, and rogiolal, a degraded derivative, of the red seaweed Laurencia microcladia from II rogiolo along the coast of tuscany: A Synergism in Structural Elucidation (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 684-694 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of rogioldiol A ((-)-1), isolated from the red seaweed Laurencia microcladia, was determined. Employing the exciton-coupling technique for rogioldiol A p-bromobenzoate (2), the absolute configuration at C(9) of (-)-1 was assigned, and, together with extensive NMR experiments, the absolute configuration at C(10) and preferred conformations of (-)-1 were determined. The absolute configuration of the hetero-substituted cyclohexane ring was deduced in analogy from the X-ray structure of 4, a derivative of the aldehyde 3, which was isolated from the same seaweed and is believed to be a degradation product of (-)-1.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800306
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  • 192
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    Synthesis and Photochromic Behaviour of Naphthopyrans, Pyranoquinolines, Pyranoquinazolines and Pyranoquinoxalines (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 725-738 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New chromenes annulated with different six-membered azaheterocycles were prepared, i.e., the 3H-pyra-no[3,2-f]quinolines 9/10 and 14, the 8H-pyrano[2,3-h]isoquinoline 11, the 8H-pyrano[3,2-f]quinazolme 12, the 8-H-pyrano[3,2-f]quinoxaline 13, and the 2H-pyrano[2,3-f]isoquinoline 15. The synthesis was achieved using conveniently substituted α,β-unsaturated aldehydes and organotitanium intermediates arising from azaheterocyclic phenols. Their photochromic behaviour (photocolouration yield, UV/VIS spectrum of photomerocyanines, rate constant of thermal bleaching) were studied besides those of corresponding naphthopyrans. The heterocycle effect and the role of substituents in the pyran moiety were investigated quantitatively through the study of the photochromic properties and the solvent effects. Diaryl-substituted azino-fused chromenes, especially isoquinoline derivatives, exhibit increased colourabilities and bathochromically shifted spectra for photomerocyanines which open up new prospects for photochromic applications.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800310
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  • 193
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    Selective N3- and 5′-O-Alkylation of 2′,3′-O-isopropylideneuridine with methyl iodide (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 851-855 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 2′,3′-O-isopropylideneuridine (1) reacts with MeI in the presence of an excess of NaH in THF giving 2′,3′-O-isopropylidene-5′-O-methyluridine (2). Prolonged reaction time gives rise to 2′,3′-O-isopropylidene-3,5′-O-dimethyluridine (4). The use of an equimolar amount of base and alkylating agent results predominantly in methylation at N(3) (→ 3).
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800319
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  • 194
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    A Short Synthesis of the Factor-Xa Inhibitor DX-9065a using palladium-catalyzed key stepsPart of the Ph. D. Thesis of C. Kehr, University of Heidelberg, 1996Dedicated to Professor Dr. Rolf Gleiter, Heidelberg, on the occasion of his 60th birthday with best wishes (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 892-896 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe a new, efficient synthesis of DX-9065a (4), a potent inhibitor of the blood coagulation enzyme factor Xa (fXa) which has previously been prepared in more than 20 steps. We saved approximately 10 steps starting with a Pd-catalyzed cyanation of the triflate 10 of 7-methoxynaphthalen-2-ol (9). After cleavage of the MeO group with boron tribromide, the triflate 6 was coupled to acrylate 5 in a Heck reaction (→3). The subsequent transformations led to DX-9065 a.
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    URL: http://dx.doi.org/10.1002/hlca.19970800322
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  • 195
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    Metal Complexes with Macrocyclic Ligands. PartXLVPart XLIV: [1] Axial coordination tendency in reinforced tetraazamacrocyclic complexes (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 948-959 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cu2+ and Ni2+ complexes of three reinforced tetraazamacrocycles, containing a piperazine subunit and one or two alkyl substituents at the other two N-atoms have been prepared and their structural properties studied. In solution, the Ni2+ complexes are square-planar and show no tendency to axially coordinate a solvent molecule or an N3- ion. In contrast, the Cu2+ complexes change their geometry depending upon the donor properties of the solvent, being square-planar in MeNO2 and pentacoordinate in DMF. They also easily react in aqueous solution with N3- to give ternary species with pentacoordinate geometry, the stabilities of which have been determined. In the solid state, the X-ray crystal structures of three Cu2+ complexes also show both geometrical arrangements, two having a square-planar, the other one a distorted square pyramidal geometry. The difference behavior of Ni2+ and Cu2+ stems from the fact that the structural change from square-planar to square-pyramidal can easily be accomplished for Cu2+, whereas, for Ni2+, it is accompanied by an electronic rearrangement from the low-spin to the high-spin configuration. The relatively rigid ligands cannot Adapt to the somewhat larger high-spin Ni2+ion.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800326
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  • 196
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    Selective Synthesis of Polyamine Derivatives: Efficient derivatization of the secondary amino group of N-monosubstituted 1,3-diaminesDedicated to Professor Klaus Schreiber on the occasion of his 70th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 966-978 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Monosubstituted 1,3-diamines were selectively functionalized at the secondary N-atom via 2-Ph-substituted hexahydropyrimidine intermediates. Reaction of the diamines with benzaldehyde, followed by treatment with an electrophile and hydrolysis, provided the desired products with excellent selectivity and in high yields. N4,N9-bis[3-phenylprop-2-enoyl]spermine (4a), which was further converted to N1,N1 2-bis[3-phenylprop-2-enoyl]spermine (15) by a transamidation reaction, was prepared by this way in 82% yield from spermine (1). Compound 4a was alternatively synthesized in 83% yield, equally from 1, by a sequence involving intermediary protection of the terminal amino groups.
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    URL: http://dx.doi.org/10.1002/hlca.19970800328
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  • 197
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    Synthesis of Monodisperse Macromolecular Bicyclic and dendriticPartially published in a preliminary communication [1] compounds from (R)-3-hydroxybutanoic acid and benzene-1,3,5-tricarboxylic acid and analysis by fragmenting MALDI-TOF mass spectroscopyDedicated to Professor Waldemar Adam on the occasion of his 60th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 989-1026 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As previously shown, oligo- and poly(β-hydroxyalkanoates) have a high tendency to form lamellar crystallites with ca. 50-Å thickness which corresponds to chain lengths of 16 units (Fig. 1). To have monodisperse model compounds, we have now prepared bicyclic derivatives with three parallel (27-29) or two parallel and an antiparallel chain (68-70) consisting of up to 16 3-hydroxybutanoate (3-HB) units. We also prepared dendritic compounds (71-75, 82-85) containing oligo(3-HB) chains which cannot possibly be arranged as in the lamellae; the branching units were prepared from trimesic acid (= benzene-1,3,5-tricarboxylic acid). So far, none of the prepared samples formed crystals or contained crystalline domains which would have been suitable for single-crystal or powder-diffraction X-ray analysis. The terminally deprotected dendrimers (74, 75, and 85) are multi-anionic (up to 12 peripheral CO2H groups) and biodegradable. The macromolecular HB derivatives (molecular weight up to 10150 Da) have been fully characterized by IR, 1H- and 13C-NMR, [α]D, and elemental analysis. Especially important is the analysis by mass spectrometry with the MALDI-TOF technique (Fig. 2), proving that the products are monodisperse; application of a new variation of this MS method (post source decay = PSD or fragment analysis by structural time of flight = FASTTM) allows for the observation of metastable fragment ions and, thus, is a tool for structural oligomer analysis (Fig. 3).
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800402
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  • 198
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    Flash Photolysis of 5-Methyl-1,4-naphthoquinone in Aqueous Solution: Kinetics and mechanism of photoenolization and of enol trappingDedicated to our colleague Fabian Gerson who is venturing to new shores (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1106-1121 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 5-Methyl-1,4-naphthoquinone (1) is a remarkable probe to study hydrogen and proton transfer reactions. The photoenol 4-hydroxy-5-methylidene naphthalen-1 (5H)-one (2) is formed in the ground state within 2 ps of excitation and with a quantum yield of unity, presumably through a conical intersection of the S0 and S1 hypersurfaces. In aqueous acid, enol 2 is hydrated to 5-(hydroxymethyl)naphthalene-1,4-diol 3 (X = OH, Scheme 1). The rate of hydration of 2 increases linearly with acid concentration from ca. 1.5 × 104 s-1 at pH 6 to reach a maximum value of 9 ×107 s-1 when the remaining carbonyl function is protonated, pKa(2+) = 1.1. Contrary to an earlier suggestion, the rate-determining step in the acid-catalyzed hydration of 2 is addition of water to the conjugate acid 2+. Pronounced acceleration of the decay rate of 2 by hydrazoic-acid buffers indicates competitive trapping of 2+ by the azide ion. In neutral-to-weakly-basic solutions, enol 2 reacts by ionization, pKa(2) = 6.5, and nearly diffusion-controlled condensation of the carbanionic species 2- with quinone 1. Proto-nation at the methylidene C-atom does not compete measurably with protonation on carbonyl O-atom, despite a Substsial thermodynamic basic for carbon Portoation of ca. 50 kJ mol-1 for 2 and 100 mol-1 for 2-.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800408
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  • 199
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    Synthesis and Evaluation of 2-{[(2-Oxo-1H-quinolin-8-yl)oxy]methyl}-Substituted α-Methylidene-γ-butyrolactones (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1161-1168 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O-Alkylation of 8-hydroxy-1H-quinolin-2-one (1) afforded 8-(2-oxopropoxy)-1H-quinolin-2-one (2) which was immediately cyclized to form the tricyclic 2,3-dihydro-3-hydroxy-3-methyl-5H-pyrido[1,2,3-de][1,4]benzoxazine,-5-one (3). The Reformatsky-type condensation of 3 furnished antiplatelet 8-[(2,3,4,5-tetrahydro-2-methyl-4-methylidene-5-oxofuran-2-yl)melhoxy]-1H-quinolin-2-one (4). Its counterparts 7a-f, Ph-substituted at C(2) of the furan ring, were obtained from 1 via alkylation and the Reformatsky-type condensation. Although compound 4 was less active against platelet aggregation than 7a-f, it was the only compound which exhibited significant inhibitory activity on high-K+ medium, Ca2+-induced vasoconstriction and was more active than most of its Ph-substituted counterparts against norepinephrine-induced vasoconstrictions.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/hlca.19970800413
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  • 200
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    Photolysis of Steroidal 20-Aryl-Substituted 11-NitritesDedicated to Prof. O. Jeger on the occasion of his 80th birthday (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 1221-1228 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The two structurally similar 20-phenyl- and 20-(4-methoxyphenyl)-11-(nitrosooxy)pregnan-20-ol derivatives 4 and 7 behave differently under photolytic conditions, the former nitrous acid ester affording, as a main product, the benzo-fused hexacyclic compound 9, and the latter the 21-nitro derivative 12. Mechanistic aspects of these transformations are discussed.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/hlca.19970800419
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