Transition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp³)-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp³)-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pK_a values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process.

过渡金属催化的不对称烯丙基取代在底物中具有适当的预先存储的离去基团，广泛用于有机合成。相比之下，对映选择性烯丙基 C(sp ³ )-H 官能化更直接，但研究较少。在这里，我们报告了长期具有挑战性的对映选择性烯丙基 C(sp ³ )-H 功能化的催化协议。通过氢化钯催化的链行走和烯丙基取代，以高产率（高达 93% 的产率）、高对映选择性（高达 98:2 er）和 100 % 原子效率。探索不同 p K _a底物的反应性值揭示了亲核试剂的合理范围和控制反应的潜在因素。一组对映体纯骨架的有效下游转换展示了该方法的实用价值。机理实验证实了 PdH 催化的不对称迁移烯丙基取代过程。