DFT computational tools and Nudged Elastic Band methods have been applied to the mechanistic analysis of a catalytic enantioselective decarboxylative allylic alkylation reaction involving a β-ketoester substrate. As illustrated in the figure, the key components of the mechanism involve (a) oxidative addition to form a tight ion pair, (b) allylic rearrangement and anion coordination that is strongly influenced by the presence of water, (c) decarboxylation, (d) facile racemization of the enolate, and finally (e) enantioselective reductive elimination. Steps (b) and (d) are particularly noteworthy. The former explains the unusually high tolerance of the reaction to water and its required presence for decarboxylation. The latter establishes that enantioselection occurs during C-C coupling.

Mechanistic analysis of a palladium-catalyzed enantioselective decarboxylative allylic alkylation reaction

253rd National Meeting (2017)

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