The cross-dehydrogenative coupling (CDC) reaction is the most direct and efficient method for constructing α-tertiary amino acids (ATAAs), which avoids the pre-activation of C(sp³)-H substrates. However, the use of transition metals and harsh reaction conditions are still significant challenges for these reactions that urgently require solutions. This paper presents a mild, metal-free CDC reaction for the construction of ATAAs, which is compatible with various benzyl C-H substrates, functionalized C-H substrates, and alkyl substrates, with good regioselectivity. Notably, our method exhibits excellent functional group tolerance and late-stage applicability. According to mechanistic studies, the one-step synthesized and bench-stable N-alkoxyphtalimide generates a highly electrophilic trifluoro ethoxy radical that serves as a key intermediate in the reaction process and acts as a hydrogen atom transfer reagent. Therefore, our metal-free and additive-free method offers a promising strategy for the synthesis of ATAAs under mild conditions.

^{交叉脱氢偶联(CDC)反应是构建α-叔氨基酸(ATAAs)最直接、最有效的方法，它避免了C(sp 3} )-H底物的预激活。然而，过渡金属的使用和苛刻的反应条件仍然是这些迫切需要解决方案的反应的重大挑战。本文提出了一种温和、无金属的 CDC 反应用于构建 ATAA，该反应与各种苄基 CH 底物、功能化 CH 底物和烷基底物兼容，具有良好的区域选择性。值得注意的是，我们的方法表现出出色的官能团耐受性和后期适用性。根据机理研究，一步合成且实验室稳定的N-烷氧基邻苯二甲酰亚胺会产生一种高亲电性的三氟乙氧基自由基，该自由基是反应过程中的关键中间体，并充当氢原子转移试剂。因此，我们的无金属和无添加剂的方法为在温和条件下合成 ATAA 提供了一种有前景的策略。