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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Steric Course of the Reaction of Enamines Derived from Open-Chain Aldehydes and Ketones with Nitro-olefins Yielding 2,3-Disubstituted 4-NitroketonesThe relative configuration of the nitro-ketone 12 obtained by the title reaction has been proved by a Baeyer-Villiger degradation and subsequent reduction to the amino-alcohol (±)-(u)-20, the relative configuration of which is identical with a sample prepared from 2-methyl-3-hydroxybutyrate of known configuration (Scheme 1). The stereochemical course of the title reaction is thus as predicted by our topological rule. It is assumed that the other nitro-ketones 13-18 described here are also formed by (lk)-combination of the trigonal centers of the educts (diastereoselectivity 〉 90%, see Formulae and Fig. 1). It is not possible to reverse this relative topicity by employing (Z)- instead of (E)-components of the starting materials, due to the reversibility of the primary step of these Michael additions (Schemes 2 and 3, and Fig. 2).
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 1822-1827 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anion-Selectivity of Distannyl Derivatives in MembranesA series of distannyl derivatives (2,2-bis(trimethylstannyl)-1,3-dithiane, 2,2-bis(tributylstannyl)-1,3-dithiane, hexamethyldistannane, hexabutyldistannane, hexaphenyldistannane, bis(triphenylstannyl)sulfide, o-bis(trimethylstannyl)benzene) has been studied in view of their applicability as anion-selective ionophores in solvent polymeric membranes. None of these compounds induces significant changes in the anion-selectivity pattern as compared with the membranes containing no organotin compound. Representatives with tributylstannyl groups, however, undergo chemical reactions leading to highly active anion ionophores of the type Bu3SnX, several of which (e.g. Bu3SnCl and Bu3SnOH) may be present in equilibrium in the membrane phase depending on the measuring conditions.
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solubility of open-chain peptide derivatives (12 examples) in non-polar, ether-type organic solvents may be greatly increased by addition of salts (LiCl, LiBr, LiI, LiBF4, LiClO4, NaI, MgBr2 CaBr2, ZnCl2) or of titanates (Ti(OEt)4, Ti(OCHMe2)4). Examples are reported (Tables 2-6) in which this solubilizing effect leads to peptide concentrations more than one-hundred-fold those in the absence of salt (cf, Boc—Ala—Gly—Gly—Gly—OH in THF from 2g·1-1 to ≥ 300 g·1-1 with 6 equiv. of LiCl), 1H-NMR Spectra of one of these solutions are reported (Fig. 1). There are no indications for epimerizations of stereogenic centres on the peptide backbone. Possible applications of these solutions in peptide chemistry are discussed.
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  • 4
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral Alkoxytitanium(iv) Complexes for Enantioselective Nucleophilic Additions to Aldehydes and as Lewis Acids in Diels-Alder ReactionsA Number of chiral 1,2-1,3 and 1,4-diols were prepared and used as alkoxy ligands on Ti for enantioselective nucleophilic transfer of methyl, butyl, cyclopropyl, allyl, alkinyl, and phenyl groups to aromatic aldehydes, as well as for the enantioselective[4+2]cycloaddition of acrylate to cyclopentadiene. The 1,2-diols were pinane diol 7 and 1,2:5.6-diacetonide-protected mannitol 9 (Scheme 3) and tartrates. The 1,3-diols were obtained from the yeast-reduction products of 2-oxocyclopentane- and 2-oxocyclohexanecarboxylates and excess MeLi, BuLi, or PhLi (or the corresponding Grignard reagents; see4-6.) As 1,4-diols, we used the products 2 and 3 from tartrate acetals and methyl or Pheny1 Grignard reagents, the bis(benzaldehyde) acetal 8 of d-mannitol and o,o'-binaphthol (22). These diols were attached to the Ti-atom by azeotropic removal of i-PrOH from a mixture with [TiCi(i-PrO)3]. Addition of various organometallic reagents R-metal (metal = Li, BR3, MgX, MnC1, CuLiR) was followed by combination with aldehydes at - 75., a warm up period, quenching with aqueous KF solution, and workup (for results see Tables 1-6 and Formulae 17-20). The enantiomeric excess of the secondary alcohols obtained varies greatly, certain combinations of chiral ligands, nucleophilic groups, and aldehyde substrates give rise to values as high as 90% ee; see e.g. Table 4. The Ti-complexes of the general formula [Ti(R*O)2Ci2] or [Ti(R*O)2(i-PrO)CI] induced the Diels-Alder addition of methyl acrylate to cyclopentadience to take place at -30.. The best enantioselectivity (50% ee) was observed with the binaphthol derivative (Table 7). The structures of the complexes involved in these reactions are unknown. The substitution on C(2) of the dioxolanes 2 and 3 (derived from tartaric acid) has a pronounced effect on the selectivities of both reactions studied here (Tables 2, 3, and 7). This remote effect (1,6-distance between the stereogenic acetal-C-atom and the Ti-centers) must be caused by conformational changes in the vicinity of the reactive site, i.e. the Ti—C bond in the nucleophilic addition reactions and the Ti-acrylate-oxygen complexation in the Diels-Alder reaction.
    Additional Material: 7 Tab.
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  • 5
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present the application of several homo- and heteronuclear 1D- and 2D-NMR techniques to assign the 1H-NMR chemical shifts of the dominant conformation of didemnin B (2; three different conformations in (D6)DMSO solution in the ratio 8:1:1) and its conformational analysis, as well as the solution conformation of didemnin A (1). The conformations were refined by restrained molecular-dynamics calculations using the GROMOS program and by MOMO, a novel personal-computer-based interactive molecular-graphics and molecular-mechanics package, using experimental distances (via a H…H pseudo potential function) as restraints. The solution structures of 1 and 2 obtained by GROMOS and MOMO calculations were compared with each other and related to the recently solved crystal structure of 2. Focusing on the main conformer, the two kinds of the distance-restrained conformational calculations for 2 yielded a ‘solution structure’ close to the crystal structure. Almost all of the 40 restrained H…H distances coincided (within the estimated standard deviations) with those observed in the crystal structure. One more hydrogen bond was detected in solution involving the lactoyl OH group (disordered in the crystal structure) and the dimethyltyrosine (Me2Tyr5) carbonyl O-atom. The macrocyclic ring system in the modeled solution structure of 1 exhibited a topology close to those of the solution and crystal structures of 2. The main difference between 1 and 2 could be traced back to a significant change in the Ψ angle of the N-methyl-D-leucine (MeLeu7) residue. In 1, the N-methyl moiety of MeLeu7 points inward within the macrocyclic ring toward the 1st and Hip region. We also tested the suitability of structures obtained from NMR data as ‘search fragments’ in the ‘Patterson search approach’ of crystal-structure analysis. It proved possible to resolve the crystal structure of 2 a posteriori with the Patterson search program PATSEE, in this way.
    Additional Material: 10 Ill.
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  • 6
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gloeosporone, the germination self-inhibitor from the fungus Colletotrichum gloeosporioides f.sp. jussiaea, is shown by spectroscopic data and X-ray analysis to have the constitution and relative configuration as shown in Formula 2 (either (1S,6R,12R)-1-hydroxy-6-pentyl-5,15-dioxabicyclo[10.2.1]pentadecan-4,13-dione or its enantiomer), rather than the previously assigned constitution 1.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 931-942 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes with Biologically Important Ligands, XXXIV. Allyl-Palladium(II) and Triphenylphosphane Gold(I) Complexes with Nucleobases and NucleosidesThe reactions of (η3-allyl)Pd(μ-Cl)2Pd(η3-allyl) (A) and (COD)Rh(μ-Cl)2Rh(COD) with nucleobases and nucleosides give the complexes (η3-C3H5)Pd(L)Cl (1) (L = inosine, adenosine, guanosine, cytosine, cytidine, 2-thiouracil, 2-thiocytosine) and (COD)Rh(cytosine)Cl (2), respectively. With adenosine and purine also ligand bridged complexes (η3-C3H5)(Cl)Pd—L—Pd(Cl)(η3-C3H5) (3) have been obtained. Ph3PAuCl reacts with the anions L′ of purine, adenine, uridine, and inosine to give the complexes Ph3PAuL′ (5). Ph3PAu+ is added to both N atoms of the dianion of uracil with formation of 6. The coordination of the nucleobases is discussed on the basis of the 1H and 13C NMR spectra. The X-ray structure of Ph3PAu(adeninate) (5b) has been determined.
    Notes: Die Umsetzung von (η3-Allyl)Pd(μ-Cl)2Pd(η3-Allyl) (A) sowie von (COD)Rh(μ-Cl)2Rh(COD) mit Nucleobasen und Nucleosiden liefert unter Spaltung der Chlorobrücken die Komplexe (η3C3H5)-Pd(L)Cl (1) (L = Inosin, Adenosin, Guanosin, Cytosin, Cytidin, 2-Thiouracil, 2-Thiocytosin) bzw. (COD)Rh(Cytosin)Cl (2). Mit Adenosin und Purin wurden auch Ligand-verbrückte Komplexe (η3-C3H5)(Cl)Pd—L—Pd(Cl)(η3-C3H5) (3) erhalten. Ph3PAuCl setzt sich mit den Anionen L′ von Purin, Adenin, Uridin und Inosin zu Ph3PAuL′ (5) um; Ph3PAu+ addiert sich an die beiden N-Atome des Dianions von Uracil unter Bildung von 6. Die Koordination der Nucleobasen wird anhand der 1H- und 13C-NMR-Spektren diskutiert. Die Struktur von Ph3PAu (Adeninat) (5b) wurde röntgenographisch bestimmt.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 889-893 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The nucleophilic substitution of chloride in dichlorocyclobutenedione by carbonylmetallates gives the μ-(3,4-dioxo-1-cyclobutene-1,2-diyl) complexes LnM(C4O2)MLn 1 [MLn=Re(CO)5, Mn(CO)5, W(CO)3(η5-C5H5)] and the μ-(2-chloro-3,4-dioxo-1-cyclobuten-1-yl) complexes LnM— [MLn = Mn(Co)5, W(CO)3(η5-C5H5), Mo(CO)3(η5-C5H5)], respectively. The structure of the dirhenium complex (OC)5Re(C4O2)Re(CO)5 (1a) was determined by X-ray diffraction. The Re-C bonds are slightly shortened with respect to single bonds, Re-C=2.18(1)/2.17(1)Å [monoclinic, P21, a=7.031(1), b=11.532(1), c=11.418(1)Å, β=105.54(1)°, V=891.95Å3, dcalc=2.727 g/cm3 for Z=2, Rw=0.031 for 252 refined parameters and 3539 observables with I ≥ 2.0σ(I)].
    Notes: Die nucleophile Substitution von Chlorid in Dichlorcyclobutendion durch Carbonylmetallate liefert die μ-(3,4-Dioxo-1-cyclobuten-1,2-diyl)-Komplexe LnM(C4O2)MLn 1 [MLn=Re(CO)5, Mn(CO)5, W(CO)3(η5-C5H5)] bzw. die μ-(2-Chlor-3,4-dioxo-1-cyclobuten-1-yl)-Komplexe LnM— [MLn = Mn(Co)5, W(CO)3(η5-C5H5), Mo(CO)3(η5-C5H5)]. Nach der Röntgenstrukturanalyse des Dirhenium-Komplexes (OC)5Re-(C4O2)Re(CO)5 (1a) sind die Re-C-Bindungen gegenüber Einfachbindungen leicht verkürzt, Re-C=2.18(1)/2.17(1)Å [monoklin, P21, a=7.031(1), b=11.532(1), c=11.418(1)Å, β=105.54(1)°, V=891.95Å3, dber=2.727 g/cm3, Z=2, Rw=0.031 für 252 verfeinerte Parameter und 3539 Observablen mit I ≥ 2.0σ(I)].
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 895-900 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (OC)5ReFBF3 reacts with ethyl thiocyanate, malononitrile, cyanamide, and dicyandiamide (L) to give the ionic complexes [(OC)5ReL]+BF-4 (1). Two or three Re(CO)-3 cations, respectively, can be added to tetracyanoethene and tetracyano-p-quinodimethane (TCNQ) to give 2, 3. With the anions of tricyanoethenolate, TCNQ-, tricyanomethanide and dicyanamide (L-) the neutral compounds (OC)5ReL (4-7) are formed. The IR spectra and the X-ray structure analyses of [(OC)5Re(NCNC(NH2)2]+BF -4 (1d), (OC)5ReNCC(CN)2 (6), and of (OC)5ReNCNCN (7) show that the ligands are coordinated in all cases via the nitrile N-atom to the metal.
    Notes: (OC)5ReFBF3 setzt mit Ethylthiocyanat, Malononitril, Cyanamid und Dicyandiamid (L) zu den ionogenen Verbindungen [(OC)5ReL]+BF-4 (1) um. An Tetracyanethen sowie an Tetracyan-p-chinodimethan lassen sich zwei bzw. drei Re(CO)-3-Kationen unter Bildung von 2 und 3 addieren. Mit den Anionen Tricyanethenolat, TCNQ-, Tricyanmethanid und Dicyanamid (L-) entstehen die Neutral-Komplexe (OC)5ReL (4-7). Die IR-Spektren sowie die Röntgenstrukturanalysen von [(OC)5Re(NCNC(NH2)2]+BF -4 (1d), (OC)5ReNCC(CN)2 (6) und (OC)5ReNCNCN (7) zeigen, daß die Liganden in allen Fällen über das Nitril-N-Atom an das Metall koordiniert sind.
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  • 10
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes with Biologically Important Ligands, XLIV. - Platinum(II) and Palladium(II) as Amino Protecting Groups. Metal Complexes with Silyl Esters and Acid Chlorides as Ligands and Peptide Synthesis at the ComplexThe cleavage of the chelate ring of platinum(II) and palladium(II) glycinate, cis-, trans-M(NH2CH2COO)2 (M = Pt, Pd), by trialkylchlorosilanes results in the formation of the complexes cis-, trans-MCl2(NH2CH2CO2SiR3)2 (1). Treatment of 1 or of cis-, trans-MCl2(NH2CHRCO2H)2, respectively, with oxalyl chloride and DMF gives the α-amino acid chloride complexes cis-, trans-MCl2(NH2CHRCOCl)2 (2) from which - using N-(trimethylsilyl)-α-amino acid esters - a series of dipeptide complexes cis-, trans-MCl2(dipeptideOR)2 (R = H, alkyl, SiMe3) (3) has been obtained. trans-Palladium complexes of type 3 and of type cis-Pd-Cl2(HisNHCHRCO2Et) (4) are also formed form the corresponding α-amino acid complexes and α-amino acid ester with a watersoluble carbodiimide.
    Notes: Der Chelatring von Platin(II)- und Palladium(II)-glycinat, cis-, trans-M(NH2CH2COO)2 (M = Pt, Pd), läßt sich mit Trialkylchlorsilanen unter Bildung der Dichlorobis(glycin-silylester)-Komplexe, cis-, trans-MCl2(NH2CH2CO2SiR3)2 (1), öffnen. Aus 1 oder den Komplexen MCl2(NH2CHRCO2H)2 werden mit Oxalylchlorid und DMF die α-Aminosäurechlorid-Verbindungen cis-, trans-MCl2(NH2CHRCOCl)2 (2) erhalten, welche mit N-(Trimethylsilyl)-α-aminosäureestern die Dipeptid-Komplexe cis-, trans-MCl2(DipeptidOR)2 (R = H, Alkyl, SiMe2) (3) liefern. trans-Palladium-Komplexe vom Typ 3 und vom Typ cis-PdCl2(His-NHCHRCO2Et) (4) entstehen auch aus den entsprechenden α-Aminosäure-Komplexen und dem α-Aminosäureester mit einem wasserlöslichen Carbodiimid.
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