Stereochemical Control in Organic-Synthesis Using Silicon-Containing Compounds

Asymmetric catalysis at chiral metal surfaces.

The oxidation of the carbon-silicon bond

Diels-Alder cycloadditions of 2-pyrones and 2-pyridones

Reserpine: A Challenge for Total Synthesis of Natural Products

Oxidative cleavage of silicon-carbon bonds in organosilicon fluorides to alcohols

Described herein are several representative examples of cleavage reactions of otherwise hardly accessible organopentafluorosilicates which are obtainable via the Diels-Alder reaction, ene reaction, and the Friedel-Crafts reaction of vinyl-, ethynyl-, or allyl-trichlorosilanes. The Diels-Alder reaction between vinyltrichlorosilane and o-xylylene generated in situ by debromination of α,α′-dibromo-o-xylene afforded (1,2,3,4-tetrahydro-2-naphthyl)trichlorosilane which was converted to the corresponding silicate. The silicate reacted with NBS and MCPBA to give the respective bromide and alcohol. The Diels-Alder reaction between ethynyltrichlorosilane and methyl coumalate gave a mixture of meta and para isomers of methyl (trichlorosilyl)benzoate in the ratio of 55/45, the silicate of which reacted with NBS to give two positional isomers of methyl bromobenzoate. The electronic effect of the methoxycarbonyl group on the Si–C bond cleavage was small. The silicate derived from 4-octenyltrichlorosilane which was obt...

Organofluorosilicates in Organic Synthesis. XVI. Synthesis of Organopentafluorosilicates via the Diels-Alder, Ene, and Friedel-Crafts Reaction. Their Transformations to Organic Halides and Alcohols

Metal catalyzed cross-coupling reactions of carbanions α to silafunctional groups. New α-hydroxyalkyl anion equivalents

Organofluorosilicates in organic synthesis. part 17. oxidative cleavage of silicon-carbon bonds in organosilicon fluorides to alcohols

Organofluorosilicates in organic synthesis. xvi. synthesis of organopentafluorosilicates via the diels-alder, ene, and friedel-crafts reaction. their transformations to organic halides and alcohols

T. Iwahara

Papers

Oxidative cleavage of silicon-carbon bonds in organosilicon fluorides to alcohols

Organofluorosilicates in Organic Synthesis. XVI. Synthesis of Organopentafluorosilicates via the Diels-Alder, Ene, and Friedel-Crafts Reaction. Their Transformations to Organic Halides and Alcohols

Metal catalyzed cross-coupling reactions of carbanions α to silafunctional groups. New α-hydroxyalkyl anion equivalents

Organofluorosilicates in organic synthesis. part 17. oxidative cleavage of silicon-carbon bonds in organosilicon fluorides to alcohols

Organofluorosilicates in organic synthesis. xvi. synthesis of organopentafluorosilicates via the diels-alder, ene, and friedel-crafts reaction. their transformations to organic halides and alcohols