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  • Alkenes
  • Wiley-Blackwell  (33)
  • American Geophysical Union
  • Blackwell Publishing Ltd
  • 1995-1999  (22)
  • 1965-1969  (11)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1557-1565 
    ISSN: 0009-2940
    Keywords: Carbonylations ; Alkenes ; Palladium ; Asymmetric catalysis ; P and N ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Palladium complexes L2PdX2 containing various group Va ligands and weakly coordinating anions are active catalysts for the carbonylation of olefin substrates. These catalytic systems, though gaining significance in industry for the synthesis of polyketones, are normally characterised by a low chemoselectivity. This derives from the numerous possibilities for initiation and termination reactions which lead to different catalytic cycles and from facile multiple alternating insertion reactions of olefins and carbon monoxide. Based on experiments carried out under conditions of low selectivity and on previously published data, the factors involved in the control of the regio-, chemo- and stereoselectivity for those reactions are discussed, taking current ideas and model studies involving the above palladium complexes into consideration.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 231-234 
    ISSN: 0009-2940
    Keywords: Diasteroselective cyclopropanation ; Copper compounds ; Homogeneous catalysis ; Molecular recognition ; Bimacrocycles ; Alkenes ; Macrocyclic ligands ; Heterocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Concave 1,10-phenanthrolines 1a-c have been used as ligands in the copper(I)-catalyzed cyclopropanation of alkenes 2 with ethyl diazoacetate. The complexes proved to be efficient cyclopropanation catalysts and exhibited an enhanced diastereoselectivity, particularly in the reactions of cyclic alkenes 2b-d. The preferred formation of exo-cyclopropanes 3b-d can be explained by the concave shape of these catalysts.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0947-3440
    Keywords: [3 + 2] Cycloadditions ; Organylseleno group transfer ; 2,3-Dihydroselenophenes ; Polysubstituted butadienes ; Selenium ; Alkenes ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (2-tert-Butylseleno)propenenitrile (12a) has been prepared and treated with dimethyl ethynedicarboxylate (3) and methyl propiolate (18) to give the 2,3-dihydroselenophenes 16 and 21, respectively. In contrast, 2-(ethylseleno)-, 2-(methylseleno)- and 2-(phenylseleno)propenenitrile (12b-d) tend to form polysubstituted butadienes 17b-d with 3 by net organoylseleno group transfer from 12b-d to C-2 of 3 following attachment of C-3 of 17 to C-3 of 3. Five-membered selenonium ylides are proposed as intermediates.
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  • 4
    ISSN: 0947-3440
    Keywords: Kinetics ; Azo couplings ; Alkenes ; Allylsilanes ; Enthalpy relationships, linear-free ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of arenediazonium ions with arenes, alkenes, allylsilanes, allylstannanes, and silyl ketene acetals have been studied in acetonitrile solution. The reactions follow second-order kinetics, and in several cases rate-determining attack of the diazonium ion has been proven by kinetic isotope effect studies (1a + 2b), by the independence of the allylsilane reactivities of the rate of desilylation (1a + 10a, d) and by the independence of the rate constants of the diazonium counterion. A decrease of the rate constant with increasing solvent donor ability (correlation with Gutmann's donor number) was found. The reactions of diazonium ions with π-nucleophiles roughly follow the correlation lgk (20°C) = s (E + N), previously derived for the reactions of carbocations with nucleophiles. With the E parameters derived for diazonium ions, rate constants for azo couplings with aromatic and nonaromatic π-nucleophiles can be predicted with an accuracy of ≈102. On the basis of E, the electrophilic reactivities of diazonium ions can be compared with those of carbocations (Figure 9), and the combination with the nucleophilicity parameters N (Figure 10) gives a first clue on possible azo coupling reactions. Literature reports are discussed within this scheme.
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  • 5
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Bidentate nitrogen ligands ; p-Quinone ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compounds of the type M(N∩N-κN)(nq)2 and M2(μ2-N∩N)(μ2-pbq)2, in which nq = 1,4-naphthoquinone, pbq = 1,4-benzoquinone, and N∩N is a monodentate or bridging ligand of the α-diimine type, were obtained from reactions of Pd(dba)2 in toluene with the 3,3′-annelated-2,2′-bipyridines: 4,5-diazafluoren-9-one (dafo) and 4,5-diazafluorene (dafe) in the presence of the appropriate p-quinone. In the corresponding reactions with 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2′-bipyrimidine (bpym), N,N′-dicyclohexyl-1,4-diaza-1,3-butadiene (chex-dab), bis[N-(o,o′-diisopropyl)phenylimino]acenaphthene (o,o′-iPr2-bian) and 5,6-dihydro-1,10-phenanthroline (dh-phen) only complexes of the type M(N∩N-κ2N)(Q) were formed (Q = nq, pbq). The structures of the complexes have been established by NMR in solution and by X-ray diffraction in the solid state; crystal structures of Pd(bpy-κ2N)(η2-pbq) (1) Pd(dafo-κN)(η2-nq)2 (14) and Pd2(μ2-dafo)(μ2,η2:η2-pbq)2 (16) have been determined. Of the ligands, dafo and dafe are the only ones apt to form complexes containing a monodentate or bridging N∩N ligand. This behaviour is ascribed to the geometrical constraints of dafo and dafe; the annelation by one carbon atom at the 3,3′-positions in these ligands causes an increase in bite angle from approximately 77° to 82°.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 91-96 
    ISSN: 1434-193X
    Keywords: Alkenes ; Electrophilic additions ; β-Sultones ; sec-Alkyl chlorosulfate ; 2-Chloro-1-alkanesulfonic acid ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -An exploratory study has been made on the reaction of a number of non-branched alkenes in [D]chloroform as an aprotic solvent, using chlorosulfuric acid as reagent both in the presence and the absence of [D8]1,4-dioxane as complexing agent. Reaction of cyclopentene (1a) with 1.1 mol-equiv. of chlorosulfuric acid in [D]chloroform in the presence of 2.2 mol-equiv. of [D8]1,4-dioxane at 0 °C yielded quantitatively 1,2-cyclopentanesultone (2a). Under similar reaction conditions, the linear alkenes 1b-g afforded the corresponding β-sultones 2b-g. The ClSO3H-dioxane complex acted as a sulfonating reagent with the alkenes to yield the corresponding β-sultones in a syn cycloaddition of SO3 to the Carbon-Carbon double bond. In the absence of [D8]1,4-dioxane the reaction of the linear alkenes 1a-1k in [D]chloroform with chlorosulfuric acid at -40 °C led to the formation of the sec-alkyl chlorosulfates 5a-i, which were formed after initial protonation of the alkene by the strongly acidic ClSO3H. Cyclopentyl chlorosulfate (5a) in [D]chloroform at 0 °C was quantitatively converted into 1,2-cyclopentanesultone (2a). The sec-alkyl chlorosulfates 5b-i at 0 °C gave rise to a mixture of the internal trans- and cis-β-sultones 2b-m. Reaction of 1-octene (1g) with both acetyl sulfate (6a) and trifluoroacetyl sulfate (6b) as reagent in [D]chloroform at -20 °C directly afforded the products 1,2-octanesultone (2g), and the (E) and (Z) isomer of 2-octene-1-sulfonic acid (4g).
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  • 7
    ISSN: 1434-1948
    Keywords: Palladium ; Bidentate nitrogen ligands ; Carbohydrates ; Alkenes ; Enantioselectivity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral N,N-chelates of formula 6-Me-pyridine-2-CH=N-R (1) and R-N=CH-CH=N-R (2) (R = 6-deoxy-α-D-glucoside or 6-deoxy-α-D-mannoside residue) and their palladium(0) complexes [Pd(N,N-chelate)(olefin)] (I) were prepared. Symmetrical type 2 ligands induced higher enantioselectivity in the coordination of prochiral olefins. The ability of a type 1 chelate to promote a stereoselective process was also assessed, i.e. dimethylfumarate inserted into the Pd-Me bond formed upon methylation of a type I complex with 50% ee. Finally, a water-soluble Pd0 complex was also prepared by deprotecting the alcoholic functions on the sugar residue, and its molecular structure determined through X-ray diffractometry.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1759-1762 
    ISSN: 1434-193X
    Keywords: Alkenes ; Cycloadditions ; Cage compounds ; Ab initio calculations ; Double-bond pyramidalization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The twofold bridged sesquinorbornenes 2 and 6 were prepared using sequential [4 + 2] cycloadditions of benzoquinone with 1,5-dihydropentalenes 1 and 5. These syntheses were improved using dilution conditions or a more reactive substituted benzoquinone. Results from semiempirical and ab initio DFT calculations indicated remarkably high pyramidalization angles (φ = 46-47°) for the central C-C double-bond atoms. The chemical reactivity with triplet and singlet oxygen, dimethyldioxirane and N-methyl-1,2,4-triazoline-3,5-dione supports these structural assignments.
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  • 9
    ISSN: 1434-193X
    Keywords: Alkenes ; Ketones ; O-O activation ; Palladium ; Zeolites ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simple ammonia complexes {cis-[PdCl2(NH3)2], [Pd(NH3)4]Cl2 or [Pd(NO2)2(NH3)2]} with copper(II) chloride and LiCl or PdII (or Pd0) inserted into zeolite (faujasite Y or mordenite Z)/CuII-LiI-Cl- precursors in anhydrous ethanol catalyse the oxidation of terminal olefins to methyl ketones by dioxygen. One oxygen atom is incorporated into the olefinic substrate, while the other is involved in a cooxidation process of the solvent leading to the formation of water. With 1-octene and ethanol, octan-2-one can be obtained selectively (up to 99 %), acetaldehyde and diethyl acetal being the main cooxidation products. Chorohydridopalladium species are key intermediates in the isomerization of 1-alkenes; it appears that the introduction of NH3, NO2- or zeolite ligands reduces the extent of isomerization and subsequently the formation of isomeric ketones (octan-3-one and octan-4-one). Although homogeneous catalysis cannot be ruled out, the improved selectivities and variations of selectivity and conversion with different zeolites suggest that a “ship-in-a-bottle” catalysis may be important.
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  • 10
    ISSN: 1434-1948
    Keywords: Hydrogenations ; Parahydrogen ; Platinum ; Alkynes ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of hydrogenation of alkynes catalyzed by the [(PR3)2PtHX]/SnX2 system (PR3 = PPh3, PMePh2; × = Cl, Br) has been studied by means of parahydrogen-induced polarization of 1H spectra (PHIP). Dihydride intermediates confirming the stepwise hydrogenation at room temperature were observed when the reaction was run in acetone. The obtained 1H-PHIP spectra, together with NMR data for related species, are consistent with the formulation of these intermediates as cis-[H2Pt(PR3)(SnX3)(σ-alkenyl)(acetone)], where the σ-alkenyl ligand originates from an insertion reaction of the alkyne (1-phenyl-1-propyne, 1-phenyl-1-butyne, diphenylacetylene, 3,3-dimethylbutyne). At elevated temperatures, the hydrogenation in acetone proceeds as a cis-synchronous transfer of the two hydrogen atoms of parahydrogen to the substrate molecule. A mechanism for this synchronous hydrogenation is suggested.
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  • 11
    ISSN: 1434-193X
    Keywords: Fluorine ; vic-Difluorination ; Fluoroalkenes ; Xenon difluoride ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vic-Difluorination proceeds by the reaction of fluoroalkenes with xenon difluoride to afford the corresponding fluorinated compounds. From the reaction with polyfluoroalkenes, the products are obtained in high to excellent yields. In this reaction, the fluorine atom substituent of alkene stabilizes the cation intermediate and suppresses side-reactions such as rearrangement.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2775-2784 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Cycloadditions ; Diatomic carbon ; Sulfones ; Alkenes ; Polycycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Chloro-1,4-benzodithiin 1,1,4,4-tetraoxide 11 is a reactive dienophile that forms Diels-Alder adducts with a number of dienes. Adducts 17a-j undergo facile dehydrochlorination to give 2,3-substituted 1,4-benzodithiin tetraoxides 18a-j, which react further with another molecule of diene (the same or a different one) affording the “double” adducts 19-23. Upon reductive desulfonylation with sodium amalgam, the latter are transformed to tetrasubstituted polycyclic olefins 24-27. These olefins correspond to the cycloadducts that would theoretically have been formed by the cycloaddition of diatomic carbon with two molecules of diene, reacting in a Diels-Alder fashion.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 2249-2255 
    ISSN: 1434-193X
    Keywords: Alkenes ; Eliminations ; Halogens ; Laser chemistry ; Photolysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehydrochlorination of 1,2-dichloropropane (DCP) was conducted by thermal elimination and CO2 laser-induced dielectric breakdown, which was induced by focusing the 10.6 μm lines of a CO2 TEA laser. Thermal dehydrochlorination proceeded by a four-centered mechanism at 〉 425 °C and by a surface-catalyzed radical process at 〈 400 °C. The product distribution of the breakdown-induced reaction at 〈 400 °C resembled that of high temperature thermal elimination and the corresponding temperature was estimated to be 〉 2000 °C.
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  • 14
    ISSN: 0947-3440
    Keywords: Mannich bases ; Quaternization ; Grob fragmentation ; Alkenes ; Nucleophilic attack ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quaternary β-amino aldehydes and β-amino ketones are cleaved in a Grob-type fragmentation induced by nucleophilic attack of NH2- on the carbonyl group of 3, to yield new carbonyl derivatives 4 and alkenes 5, and unsaturated amides 6, respectively.
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  • 15
    ISSN: 0947-3440
    Keywords: Electron transfer reactions ; Radical additions ; 1,3-Asymmetric induction ; Alkenes ; γ-Lactones ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkyl 2-iodoalkanoates 2, and 2-iodoalkanenitriles 15 were added, with copper powder, to the 1-alkenes 1a, e, f, and h, and to the alkenes 1b, c, d, and g with a 1,2-dialkyl substituted double bond, to give, respectively, γ-lactones and 4-iodoalkanenitriles in very good yields. No solvent was used. The reaction is a free radical addition initiated by electron transfer from copper to the activated iodoalkane. Yields were lower using the respective bromo compounds. In situ formation of the iodo compounds, by addition of stoichiometric amounts of sodium iodide to the reaction mixture, gave improved yields. In the case of the methyl bromomalonates 6, the addition of sodium iodide proved to be unnecessary. The diastereoselectivity of the addition reaction by relative 1,3-asymmetric induction was rationalized by consideration of the steric interactions of the substituents in the transition state which is formed in the process of iodine transfer to the chiral adduct radical.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2885-2896 
    ISSN: 1434-193X
    Keywords: Alkenes ; Alkynes ; Cycloadditions ; Nitrogen heterocycles ; Tetrazines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Full details on the reactivity of the title compound as 4π component in inverse-type Diels-Alder reactions, including kinetic data, are reported. Donor-substituted alkynes, alkenes, donor-substituted and unsubstituted cycloalkenes, ketene acetals and aminals, as well as several cyclic enol ethers were used as dienophiles in these investigations. A number of 4-mono- and 4,5-disubstituted pyridazines can easily be obtained by this method.
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  • 17
    ISSN: 1434-193X
    Keywords: Alkenes ; Methylthiomethyl sulfone ; Carbenoids ; Hetero-substituted carbanions ; Vinyl sulfides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The reaction of methylthiomethyl p-tolyl sulfone with alkyl sulfones when lithiated gives regioselectively vinyl sulfides in high yields in the presence of Ni(acac)2 or Fe(acac)3.
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  • 18
    ISSN: 1434-193X
    Keywords: Hydrogen transfer ; Zirconium ; Alkenes ; Isobutylzirconocene chloride ; Lewis acid catalysis ; Lewis acid catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The hydrozirconation reaction of monosubstituted alkenes with iBuZrCp2Cl can be significantly accelerated by catalytic amounts of various Lewis acidic metal compounds, most notably AlCl3, Me3SiI, and Pd complexes, such as Li2PdCl4 and Cl2Pd(PPh3)2.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/99042_s.pdf or from the author.
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  • 19
    ISSN: 1434-193X
    Keywords: Alkenes ; Chirality ; Longicorn beetle ; Pheromones ; Psacotheahilaris ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Both the enantiomers of (Z)-21-methyl-8-pentatriacontene (1), the major component of the female-produced contact sex pheromone of the yellow-spotted longicorn beetle (Psacotheahilaris), were synthesized by starting from the enantiomers of citronellol (2)
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  • 20
    ISSN: 1434-193X
    Keywords: Alkenes ; Epoxidation ; Manganese ; Porphyrins ; Catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of MnIII porphyrins progressively halogenated in the β-pyrrolic positions was employed to catalyse the epoxidation of cis-stilbene by iodosylbenzene, and to study the role of the electronic effects on the stereoselectivity of this process. A gradual improvement in the stereoselectivity on increasing the number of β-halogen atoms was observed. The role of steric effects upon the epoxidation was also investigated by placing ortho-substituents in the meso-phenyl rings, and it was found that steric effects are more important than electronic effects toward the stereoselectivity of this process. These results can be rationalised by proposing a competition between a nonstereoselective electrophilic pathway of addition and a stereospecific pathway of oxygen insertion, the former being disfavoured by electron-withdrawing substituents. Alternatively, the formation of an open intermediate between the MnV oxene and the substrate could be suggested, where the stereoselectivity ought to be determined by the competition between closure of the epoxide ring and rotation around the C-C bond. In this case, the enhanced stereoselectivity given by our polyhalogenated porphyrins might be attributed to an acceleration of the epoxide ring closure caused by the electron-withdrawing effect of the halogen substituents.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 7 (1968), S. 247-252 
    ISSN: 0570-0833
    Keywords: Reduction ; Chromium ; Alkyl halides ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chromium(II) salts can be used for a variety of reductions in organic chemistry; for example, alkyl halides and suitably substituted olefins may both be reduced to alkanes, and alkynes may be converted into trans-olefins. Several epoxyketones are reduced to α,β-unsaturated ketones or β-hydroxyketones, and a nitro steroid was found to give a hydroxy(hydroxyimino) compound. The reduction of alkyl halides is reported to proceed by a free-radical mechanism; the halogen atom that is set free forms a bridge between two chromium atoms.
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  • 22
    ISSN: 0570-0833
    Keywords: Carbonylation ; Alkenes ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During a search for catalysts that allow carbonylation reactions on olefins to proceed below 100 °C, complex palladium(II) compounds having the formula LmPdXn were found to be catalytically active. L denotes a ligand such as a phosphine, nitrile, amine, or olefin, X is an acid residue, and m+n is 3 or 4. The catalysts permit the carbonylation of heat-sensitive compounds, as well as selective carbonylation of polyunsaturated olefins. The new process can also be carried out on the industrial scale, as is shown by the carbonylation of cyclododecatriene
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  • 23
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 7 (1968), S. 754-765 
    ISSN: 0570-0833
    Keywords: Electron-rich alkenes ; Tetraaminoethylen ; Alkenes ; Tetramethoxyethylene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Olefins are normally preferentially attacked by electrophiles. This trend is strengthened in enol ethers and enamines, and is particularly pronounced in tetramethoxyethylene and in tetraaminoethylenes. These electron-rich olefins are accordingly also excellent reducing agents. In their reactivity, therefore, they behave as counterparts of tetracyanoethylene. This compound shares with the electron-rich olefins a strong tendency to undergo cycloadditions, the electron-rich olefins adding particularly readily to electrophiles.
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  • 24
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 4 (1965), S. 49-68 
    ISSN: 0570-0833
    Keywords: Elimination ; Alkenes ; Alkynes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eliminations from olefins are very often initiated by bases, and usually lead to formation of acetylene derivatives. In view of the numerous side-reactions and subsequent additions or rearrangments observed, the nature of the base used is of considerable significance. Organometallic bases are very versatile. In addition to dehydrohalogenation, dehalogenation by metals, and also thermolytic and photolytic eliminations. (e.g. the retrodiene reaction with exchange of substituents) are discussed. Elimination from low-membered cyclic olefins yields cycloalkynes having strained ring-systems, and the existence of these can be demonstrated by trapping them. The mechanisms known for β-elimination (E2, E1 and E1cB) occur also in the case of olefins; however - due to the sp2-hybridization of the carbon atoms taking part - they are realized with different rates of reaction relative to saturated compounds. α-Eliminations from olefines having aryl residues in the β-position lead to formation of arylacetylenes by rearrangement of the carbon skeleton. The mechanism of this reaction, which is known as the Fritsch-Buttenberg-Wiechell rearrangement, is discussed in considerable detail, and several variations of the reaction are considered. According to present-day knowledge carbenes are involved in α-eliminations only when both β-positions of the olefin are occupied by aliphatic substituents, or when they are occupied by aromatic residues where rearrangement to acetylenes is impossible for steric reasons (as for example with 9-chloromethylenefluorene). With organolithium compounds a number of dehydrohalogenations, which are formally β-eliminations, actually proceed via deprotonation on the halogenbearing carbon atom (α-metallation). α-Metallations are the rate-determining steps when ether is used as solvent, but proceed quickly in tetrahydrofuran even at low temperatures. Compounds of the type \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$\raise1pt\hbox{$〉$}{\rm C}\raise1pt\hbox{=\kern-3.45pt=}{\rm C(Li)Cl}$\end{document} may be prepared by this method and are recognized as intermediates in α-eliminations.
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  • 25
    ISSN: 0570-0833
    Keywords: Allyl transition metal systems ; Bis(allyl)nickel ; Nickel ; Polymerization ; Alkenes ; Allylic ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As a continuation of a report published in 1963, recent results in the field of allyl-transition metal complexes are describedThe term “allyl compounds” in the present paper refers not only to compounds containing the simple allyl group (CH2=CH—CH2—), but also to those that contain substituted allyl groups or allyl groups forming part of a ring system.. Syntheses and reactions of these compounds, as well as the bonding between metal and allyl group, are discussed. Allyl-transition metal complexes form the basis of extremely selective catalysts for homogeneous reactions of 1, 3-diolefins and of olefins; the metal atoms in these “matrix” catalysts are either “bare”The description “bare” is applied to complexed metal atoms from which the ligands can be quantitatively displaced by the substances taking part in catalytic reactions. or are bound to only a few ligands.
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  • 26
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 6 (1967), S. 423-434 
    ISSN: 0570-0833
    Keywords: Addition ; Alkenes ; Alkynes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The possibilities of additions to the activated CC triple bond are discussed with the aid of a number of examples. The additions of donors that contain no active hydrogen are generally initiated via a dipolar primary complex, which can undergo stabilization by rearrangement, cyclization, or addition reactions. Preparative aspects of these reactions are also discussed. They offer routes for the preparation of heterocycles, particularly pyrrole and thiophene derivatives.
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  • 27
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 4 (1965), S. 583-587 
    ISSN: 0570-0833
    Keywords: Alkylidenephosphoranes ; Phosphonium salts ; Synthetic methods ; Phosphoranes ; Ylides ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phosphonium salts may be regarded as Bronsted acids, and alkylidenephosphoranes as the conjugate bases. Compounds of the two classes exist in equilibrium with each other. Phosphonium salts and alkylidenephosphoranes can be obtained by this “transylidation”. Other methods are also given for the preparation of members of both classes.
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  • 28
    ISSN: 0570-0833
    Keywords: Alkylidenephosphoranes ; Phosphonium salts ; Synthetic methods ; Phosphoranes ; Ylides ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of alkylidenephosphoranes with compounds containing halogens can be used to prepare ylides, which can be converted in to useful products, e.g. by hydrolysis, by thermal decomposition, or by other reactions. Examples of such products are ketones including cyclic, unsaturated, and branched-chain ketones (including cyclic, unsaturated, and branched-chain ketones), carboxlic esters (including those of unsaturated, branched- chain, polyenecarboxylic, acetylenecarboxylic, and allenecarboxylic acids), and aldehydes.
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  • 29
    ISSN: 0570-0833
    Keywords: Alkylidenephosphoranes ; Phosphonium salts ; Synthetic methods ; Phosphoranes ; Ylides ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A few examples of preparatively useful syntheses using alkylidenephosphoranes and substances containing a C—N or C—C double bond are the preparations of olefins, allenes, pyran derivatives, and cyclopropane derivatives. Olefins, ketones, and monocyclic compounds can be obtained by autoxidation of alkylidenephosphoranes; α, β-dioxo compounds (including cyclicones) can be prepared by oxidation with peroxy-acids. Alkylidenephosphoranes can also be used for the synthesis of azines and Schiff bases. Of the many possibilities offered by the Wittig reaction, only the preparation of tritiated aldehydes and olefins will be considered.
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  • 30
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 241-270 
    ISSN: 0570-0833
    Keywords: alkenes ; asymmetric syntheses ; Horner-Wittig reactions ; phosphane oxides ; synthetic methods ; Alkenes ; Asymmetric synthesis ; Horner-Wittig reaction ; Phosphane oxides ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1959, Horner showed that metalated alkyldiphenylphosphane oxides react with aldehydes or ketones to give alkenes. With this reaction, the diphenylphosphoryl (Ph2PO) group made its entrance into synthetic organic chemistry. In the thirty-six years since that date, extensive research has shown that this olefination, the Horner-Wittig reaction, has unique properties that make it much more than simply the phosphane oxide cousin of the more famous phosphorus-based olefinations - the Wittig reaction (based on phosphonium salts) and the Wadsworth-Emmons reaction (based on phosphonate esters). Early work on the Horner-Wittig reaction concentrated on the reactivity of phosphane oxides and the regioselectivity of their reactions, but more recently the power of the Ph2PO group to control the stereochemistry of alkenes, and to produce “on demand” either stereoisomer in high stereochemical purity, has emerged. From the study of these stereocontrolled Horner-Wittig reactions arose the realization that the Ph2PO group is useful not only for the control of the two-dimensional stereochemistry of alkenes, but also of three-dimensional stereochemistry in general.After a brief introduction to phosphane oxide chemistry, this review will examine the Horner-Wittig reaction, in both its original and “stereocontrolled” varieties. From there, we will move on to an account of the stereoselective construction of molecules containing the Ph2PO group, concentrating on the stereochemical directing effects of the Ph2PO group and on the role of its unique combination of attributes - steric bulk, electronegativity, and Lewis basicity - in controlling these reactions. Finally, we will present what is intended as a practical guide to this chemistry, covering the type of functionalized alkenes that have been made with the help of the Ph2PO group and giving guidelines that we hope will help the organic chemist to make the most of the chemistry the Ph2PO group has to offer.
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  • 31
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 8 (1969), S. 556-577 
    ISSN: 0570-0833
    Keywords: Ene reaction ; Addition ; Alkenes ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ene reaction is defined as the indirect substituting addition of a compound with a double bond (enophile) to an olefin with an allylic hydrogen (ene). For a long time the reaction has been neglected and has remained overshadowed by the related Diels-Alder addition. It is shown that the ene reaction possesses wide scope and applicability ranging from industrial to biosynthetic processes. Preparative aspects are summarized and current views on the mechanism are discussed.
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  • 32
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 7 (1968), S. 903-911 
    ISSN: 0570-0833
    Keywords: Alkylation ; Squalene epoxide ; Polyisoprenoid synthesis ; Biosynthesis ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereochemical studies, made possible by asymmetric labeling with hydrogen isotopes, have led to the hypothesis that enzymic association of C5 units in polysoprenoid synthesis is not a concerted process but proceeds in two steps: a trans 1,2-addition to an olefin followed by a trans 1,2-elimination. It is shown that similar mechanisms can also explain the cyclization of squalene epoxide to tetracyclic and pentacyclic triterpenoids.
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  • 33
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    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 2442-2469 
    ISSN: 0570-0833
    Keywords: alkenes ; carbonyl compounds ; heterocycles ; McMurry reactions ; titanium compounds ; Alkenes ; Carbonyl compounds ; Heterocycles ; McMurry reaction ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Among the applications of low-valent titanium in organic synthesis, the reductive coupling of carbonyl compounds to produce alkenes (the McMurry reaction) is particularly prominent. Discovered at the beginning of the 1970s, it has been developed and tested repeatedly, for example in numerous syntheses of natural products. This alkene synthesis has become a standard reaction in the repertoire of preparative chemists. However, the possibilities of low-valent titanium are by no means limited to this process: the last few years have brought some spectacular applications of the conventional McMurry reaction (for example the synthesis of taxol) along with a considerable extension of the scope of reductive carbonyl couplings. Thus, diverse heterocycles are now accessible following novel and efficient pathways based on intramolecular cross-coupling of functional groups - some of which were hitherto considered to be inert to titanium. The use of this method for the synthesis of indole and pyrrole alkaloids illustrates the new possibilities. At the same time, considerably simplified methods for conducting McMurrytype reactions have been developed. Examples include the particularly convenient “instant” method, the first ketone-amide coupling reactions requiring only catalytic amounts of titanium salts, and the first application of commercially available titanium powder as a coupling agent. Last but not least, the detailed investigation of diverse classical McMurry reagents has afforded a deeper understanding of the nature and mode of action of low-valent titanium. Revision of some of the current conceptions of the process of reductive carbonyl coupling is thus indispensable.
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