In contrast to the wealth of enantioselective prochiral C(sp³)–H functionalization that is transition-metal-catalysed, the enantioconvergent transformation of racemic tertiary C(sp³)–H bonds (pK_a > 25) still represents a vastly uncharted domain. The mechanistic limitation is partial or complete chirality retention, which is inherent to developed enantioselective C–H functionalization catalysis and poses the major challenge in establishing such a process. To this end, we herein describe the combination of decoupled hydrogen atom abstraction with asymmetric copper catalysis for enantioconvergent tertiary β-C(sp³)–H amination of racemic ketones. This method, when allied with follow-up transformations, provides facile access to a range of enantioenriched compounds featuring quaternary stereocentres. We anticipate that this work will inspire the future design of generally efficient catalysts for enantioconvergent transformations of racemic tertiary C(sp³)–H bonds.

与过渡金属催化的大量对映选择性手性C（sp ³）-H功能化相反，外消旋叔C（sp ³）-H键的对映体转化（p K _a  > 25）仍然是一个未知数域。机械学上的局限性是部分或全部手性保留，这是开发的对映选择性CHH功能化催化所固有的，并在建立这样的过程中提出了重大挑战。为此，我们在此描述解耦氢原子提取与不对称铜催化的对映收敛的叔β-C（sp ³）–外消旋酮的H胺化。与后续转换相关联时，该方法可轻松访问一系列具有四级立体中心的对映体富集化合物。我们预计这项工作将启发未来设计外消旋叔C（sp ³）-H键对映体转化的一般有效催化剂。