The direct ortho‐alkynylation of substituted phenylalanine has been successfully achieved through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C‐H functionalization. This innovative protocol showcases the ability to apply a diverse range of phenylalanine substrates, resulting in the efficient synthesis of alkynylation benzylamine derivatives with notable effectiveness. Computational investigations further revealed that the fluoride ion enhances the electropositivity of Pd(IV) and the interaction between C1 and C2 within the transition state of the reductive elimination, which significantly expedites the reductive elimination step in the alkynylation process.

中文翻译：

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Pd 催化 MIA 定向苯丙氨酸邻位 C-H 烷基化的实验与计算研究

通过甲氧基亚氨基酰基（MIA）介导的 Pd 催化的 C-H 官能化，已成功实现取代苯丙氨酸的直接邻炔化。这种创新方案展示了应用各种苯丙氨酸底物的能力，从而有效合成具有显着效果的炔基化苄胺衍生物。计算研究进一步表明，氟离子增强了 Pd(IV) 的电正性以及还原消除过渡态下 C1 和 C2 之间的相互作用，从而显着加快了炔基化过程中的还原消除步骤。