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Intermolecular Chirality Transfer from Silicon to Carbon:  Interrogation of the Two-Silicon Cycle for Pd-Catalyzed Hydrosilylation by Stereoisotopochemical Crossover

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journal contribution
posted on 24.01.2007, 00:00 by Sebastian Rendler, Martin Oestreich, Craig P. Butts, Guy C. Lloyd-Jones
A “two-silicon cycle” for the highly efficient intermolecular chirality transfer from silicon to carbon (98−99% ct) in the palladium-catalyzed hydrosilylation of norbornenes emerges from an investigation involving catalytic crossover experiments with isotopically labeled silicon-stereogenic silanes. A key outcome of these experiments, which are supported by product-distribution modeling, is the conclusion that the chirality transfer arises from thermodynamically controlled reversible silapalladation of the alkene rather than from kinetic control during irreversible σ-bond metathesis of the resulting β-silyl σ-alkyl palladium complex with chiral silane.