Regioselective hydrosilylation-desilylation: convenient preparation of a 2-(trimethylsilyl)-1-alkene (original) (raw)
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ChemInform Abstract: HYDROSILYLATION REACTION OF DICYCLOPENTADIENE
Chemischer Informationsdienst, 1980
Bei der durch Platinchlorwasserstoffsäure katalysierten Anlagerung der Silane (II) an Dicyclopentadien (I) können sich Anlagerungsprodukte sowohl an der 1,2‐Doppelbindung wie (III) als auch an der 9,10‐Doppelbindung wie (IV) bilden.
Palladium-catalyzed hydrosilylation of silyl-substituted butadienes
Heteroatom Chemistry, 1995
Palladium-catalyzed hydrosilylation of silyl-substituted butadienes 1 and 2 with MeSiC12H has been investigated. Both steric effects and the presence of a n aiyl substituent affect the regiochemistry of the hydrosilylation reaction. Hydrosilylation of siloxanetethered bis-dienes 9 exhibits high regio-and diastereoselectivity .
This is the sixth chapter in the series published by the same authors: “The Organic Chemistry Notebook Series, a Didactical Approach”. Here we offer the mechanistic views of the synthesis of alkenes by oxidative decarboxylation of carboxylic acids. The aim of this series of studies is to help students to have a graphical view of organic synthesis reactions of diverse nature. The oxidative decarboxylation of carboxylic acids is a useful method for generating alkenes. Here we propose the mechanism and its discussion for the application of the method of decarboxylation of diacids lacking nearby double bonds. Also, the route is explained mechanistically for the preparation of Dewar benzene. The thermal or photolytic decomposition of di-t-butyl per-esters is described. The treatment of monocarboxylic acids to afford alkenes in the presence of lead tetraacetate and copperII acetate is briefly discussed. The alkylation-decarboxylation of aromatic acids is also explained. The oxidative decarboxylation of carboxylic acids can eventually conduct to the obtaining of ketones instead of alkenes. We have used a series of reactions reviewed by W. Carruthers, and we have proposed didactical and mechanistic views for them. This latest approach is included in the synthetic methods reviewed by W. Carruthers with respect to the “Formation of carbon-carbon double bonds”. Spanish title: Síntesis de alquenos por descarboxilación de ácidos carboxílicos; vistas mecanísticas; De la serie: El cuaderno de notas de química orgánica, un enfoque didáctico, Nº6.
The Journal of Organic Chemistry, 2005
The catalytic hydrosilylation of highly hindered and functionalized ketones is described. The combination of inexpensive catalyst precursors, CuCl and NHC‚HX (NHC) N-heterocyclic carbene), leads to a highly efficient reduction mediator for the preparation of silyl ethers from unfunctionalized and functionalized alkyl, cyclic, bicyclic, aromatic, and heteroaromatic ketones. A series of catalyst precursors have been structurally characterized and a catalyst-structure activity relationship is discussed.
Tetrahedron, 1989
On the basis of our observation that (E)-1-bromo-1-alkenes undergo preferentially stereospecific Pd-catalyzed cross-couplings with a variety of organometallics, in the presence of the corresponding (Z)-stereoisomers, efficient and convenient cliastereoselective procedures have been developed to prepare nearly stereoisomerically pure (E)-1-trimethylsilyl-2-alkenes (4). (E)-ltrimethylsilyl-1-alken-3-ynes (5). (lE, 5E)-l-trimethylsilyl-lJ-alkadien-3-ynes (6). and (lE,3E)-ltrimethylsilyl-1.3~alkadienes (8) from stereoisomeric mixtures of alkenyl bromides. Compounds 5 have been stereoselectively converted into (lE.32)-1-trimethylsilyl-13dienes (7) by selective hydrometallations. followed by hydrolysis. Some synthetic applications of compounds 5-8 have been also examined.
Hydroxysulfonylation of alkenes: an update
RSC Advances
The direct difunctionalization of alkenes recognized as a straightforward tool for the rapid fabrication of complex molecules and pharmaceutical targets by introducing two different functional groups on adjacent carbon atoms of common alkene moieties.
Tetrahedron, 2014
a b s t r a c t 1,1,3,3-Tetramethyldisiloxane (TMDS) is a highly reactive reducing reagent in the Au/TiO 2 -catalyzed hydrosilylation of carbonyl compounds relative to monohydrosilanes. The reduction of aldehydes or ketones with TMDS can be performed on many occasions at ambient conditions within short reaction times and at low loading levels of gold, whereas typical monohydrosilanes require excess heating and prolonged time for completion. The product yields are excellent, while almost stoichiometric amounts of carbonyl compounds and TMDS can be used. It is postulated that the enhanced reactivity of TMDS is attributed to the formation of a gold dihydride intermediate. This intermediate is also supported by the fact that double hydrosilylation of carbonyl compounds by TMDS is a negligible pathway.