- Vinyl polymerization versus [1,3] O to C rearrangement in the ruthenium-catalyzed reactions of vinyl ethers with hydrosilanes
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Two reactions, vinyl polymerization and [1,3] O to C rearrangement of vinyl ethers, are investigated in the ruthenium-catalyzed reaction with hydrosilanes. The reaction pathways are dependent on the substituents of the vinyl ether, in particular, those of the alkoxy group. Primary-, secondary-, and tertiary-alkyl vinyl ethers, ROCHCH2, are polymerized with ease to give the corresponding polymer in good yields. When R is electron-donating benzyl groups, the reaction does not give the polyvinyl ether but results in [1,3] O to C rearrangement to give the corresponding aldehyde, RCH2CHO in moderate to good yields. The rearrangement selectively proceeds when vinyl ethers having α-substituents are used as the starting materials to give the corresponding ketones in high yields. With catalytic amounts of hydrosilanes, the rearrangement gives ketones or aldehydes selectively. In sharp contrast, use of excess amounts of hydrosilanes leads to the rearrangement followed by reduction of the formed carbonyl group to give the corresponding silyl ethers in good yields. Nature of catalytically active species is discussed. Crown Copyright
- Harada, Nari-Aki,Nishikata, Takashi,Nagashima, Hideo
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supporting information; experimental part
p. 3243 - 3252
(2012/06/01)
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- Catalyzed Reactions of Enol Ethers with SN1 Active Groups: A Novel Method for the Preparation of α-Alkylated Ketones
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The performance of tert-alkylations, alkoxyalkylations, and aldehyde enolate allylations proceeding with low catalyst loading (0.1 mol % - 5 mol %) is described. The reactions are complete within short times and can even be performed without solvent and under ambient conditions. The mechanism of the reaction was investigated by deuterium labeling and cross-over studies.
- Gansaeuer, Andreas,Fielenbach, Doris,Stock, Christoph,Geich-Gimbel, Daniel
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p. 1017 - 1030
(2007/10/03)
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- Triisobutylaluminium promoted reductive rearrangement of substituted vinyl ethers to homologous alcohols
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Substituted vinyl ethers carrying electron-donating groups in the ether moiety undergo smooth oxygen to carbon rearrangement with triisobutylaluminium to afford chain extended alcohols.
- Du Roizel,Sollogoub,Pearce,Sinay
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p. 1507 - 1508
(2007/10/03)
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