Catalytic asymmetric functionalization of unstrained C(sp³)–C(sp³) bonds is a promising strategy to edit the structure of a molecule stereoselectively, but such reactions are rare. Existing methods for the catalytic functionalization of C–C bonds typically involve C–C bonds in strained structures. Here we report a strategy to achieve unexplored enantioselective functionalizations of allylic C(sp³)–C(sp³) bonds. Protocols for both kinetic resolution and dynamic kinetic asymmetric transformation are established to construct new C–C bonds at the position of a C(sp³)–C(sp³) bond in the reactant. This study shows that enantioselective functionalizations can be achieved even at unstrained C–C bonds, and an alkyl C–C bond can also work as a leaving group instead of a stable product in enantioselective allylic substitution reactions. Mechanistic experiments and density functional theory calculations reveal that deracemization by the formation of dienes enables the process to occur as a dynamic kinetic asymmetric transformation.

无应变 C(sp ³ )–C(sp ³ ) 键的催化不对称官能化是立体选择性编辑分子结构的一种有前景的策略，但此类反应很少见。现有的 C-C 键催化功能化方法通常涉及应变结构中的 C-C 键。在这里，我们报告了一种实现烯丙基 C(sp ³ )–C(sp ³ ) 键的未探索的对映选择性官能化的策略。建立了动力学拆分和动态动力学不对称转化的协议，以在 C(sp ³ )–C(sp ³ ) 键位置构建新的 C-C 键反应物。这项研究表明，即使在无张力的 C-C 键上也可以实现对映选择性官能化，并且烷基 C-C 键也可以在对映选择性烯丙基取代反应中作为离去基团而不是稳定产物。机理实验和密度泛函理论计算表明，通过形成二烯进行去外消旋化使得该过程能够以动态动力学不对称转变的形式发生。