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Conformational rigidity of silicon-stereogenic silanes in asymmetric catalysis: A comparative study.

ABSTRACT: In recent years, cyclic silicon-stereogenic silanes were successfully employed as stereoinducers in transition metal-catalyzed asymmetric transformations as exemplified by (1) the hydrosilylation of alkenes constituting a chirality transfer from silicon to carbon and (2) the kinetic resolution of racemic mixtures of alcohols by dehydrogenative silicon-oxygen coupling. In this investigation, a cyclic and a structurally related acyclic silane with silicon-centered chirality were compared using the above-mentioned model reactions. The stereochemical outcome of these pairs of reactions was correlated with and rationalized by the current mechanistic pictures. An acyclic silicon-stereogenic silane is also capable of inducing excellent chirality transfer (ct) in a palladium-catalyzed intermolecular carbon-silicon bond formation yet silicon incorporated into a cyclic framework is required in the copper-catalyzed silicon-oxygen bond forming reaction.

SUBMITTER: Rendler S

PROVIDER: S-EPMC1810299 | biostudies-literature | 2007 Feb

REPOSITORIES: biostudies-literature

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Conformational rigidity of silicon-stereogenic silanes in asymmetric catalysis: A comparative study.

Rendler Sebastian S Oestreich Martin M

Beilstein journal of organic chemistry 20070208

In recent years, cyclic silicon-stereogenic silanes were successfully employed as stereoinducers in transition metal-catalyzed asymmetric transformations as exemplified by (1) the hydrosilylation of alkenes constituting a chirality transfer from silicon to carbon and (2) the kinetic resolution of racemic mixtures of alcohols by dehydrogenative silicon-oxygen coupling. In this investigation, a cyclic and a structurally related acyclic silane with silicon-centered chirality were compared using the ...[more]

PMID: 17288605

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