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The mechanism of Pd-catalyzed enantioselective allylic alkylation involves two steps which are of major importance in the catalytic cycle. [1] First, the allylic substrate, usually in the Scheme 2. Preferential formation of the product with S configuration. The methyl groups at C11 and C32 are represented by black circles, and the Pd atom by a gray circle. nated between C1 and C3, which otherwise differ little in their steric and electronic properties.

Preferential rotation in substrate-palladium intermediates in a catalyzed asymmetric allylic alkylation is proposed to be responsible for both the observed kinetic resolution of the racemic allylic acetate starting material as well as the high selectivity found in the enantiodiscriminating product-forming step [Eq. (a)].