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.