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. Author manuscript; available in PMC: 2025 Mar 20.
Published in final edited form as: J Am Chem Soc. 2024 Mar 7;146(11):7165–7172. doi: 10.1021/jacs.4c00564

Figure 4.

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.