Figure 4.
Kinetic studies and computational analysis of K-3f–catalyzed olefination. (A) Same-excess experiments revealing evidence for inhibition by the OPA product. (B) Different-excess experiments consistent with first-order kinetic dependence on [ylide] and a shift from zero-order to positive-order dependence on [ketone] over the course of the reaction. (C) First-order kinetic dependence on [K-3f]T. (D) Absence of nonlinear effect. (E) Proposed catalytic cycle. (F) Proposed rate law and fitted kinetic parameters. (G) Computational analysis of enantiodetermining step reproduces experimental selectivity.
