Counterintuitive Kinetics In Tsuji-trost Allylation: Ion-pair Partitioning And Implications For Asymmetric Catalysis

摘要

The Tsuji-Trost allylation of stabilized carbanions (1 + 2 → 3, Scheme 1) has evolved from a stoichiometric process into one that is catalytic, versatile, and extraordinarily selective. The generic catalytic cycle outlined in Scheme 1, involving oxidative addition (k_(OA) → [4]~+), followed by nucleophilic attack (κ_(Nu)) has become firmly established in the literature. The apparent simplicity of the mechanism and general robustness of the process accounts for its ubiquity as a "benchmarking reaction" in ligand design for asymmetric catalysis. Herein we report on the kinetics of the catalytic reaction in the absence of interfering coligands such as halide or dba.