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. 2007 Feb 8:3:9.
doi: 10.1186/1860-5397-3-9.

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

Sebastian Rendler  1 , Martin Oestreich
Affiliations

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

Sebastian Rendler et al. Beilstein J Org Chem. .

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.

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Figures

Figure 1
Figure 1
Cyclic and acyclic sterically encumbered silanes.
Scheme 1
Scheme 1
Cyclic and acyclic chiral silanes as potent reagents for the silicon-to-carbon chirality transfer.
Scheme 2
Scheme 2
Kinetic resolution of secondary alcohols using a dehydrogenative coupling reaction.
Scheme 3
Scheme 3
Catalytic cycle for hydrosilylation.
Scheme 4
Scheme 4
Postulated catalytic cycle for dehydrogenative coupling.
See this image and copyright information in PMC

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