In contrast with the well-established enantioconvergent radical C(sp³)–C cross-coupling of racemic secondary alkyl electrophiles, the corresponding coupling of tertiary electrophiles to forge all-carbon quaternary stereocentres remains underexplored. The major challenge arises from the steric hindrance and the difficult enantio-differentiation of three distinct carbon substituents of prochiral tertiary radicals. Here we demonstrate a general copper-catalysed enantioconvergent C(sp³)–C(sp) cross-coupling of diverse racemic tertiary alkyl halides with terminal alkynes (87 examples). Key to the success is the rational design of chiral anionic N,N,N-ligands tailor-made for the computationally predicted outer-sphere radical group transfer pathway. This protocol provides a practical platform for the construction of chiral C(sp³)–C(sp/sp²/sp³) bonds, allowing for expedient access to an array of synthetically challenging quaternary carbon building blocks of interest in organic synthesis and related areas.

与外消旋仲烷基亲电试剂的对映收敛自由基 C( sp ³ )-C 交叉偶联相反，三级亲电试剂的相应偶联以形成全碳四元立体中心仍未得到充分探索。主要挑战来自前手性叔自由基的三个不同碳取代基的空间位阻和困难的对映体分化。在这里，我们展示了各种外消旋叔烷基卤化物与末端炔烃的通用铜催化对映收敛 C( sp ³ )–C( sp ) 交叉偶联（87 个例子）。成功的关键是手性阴离子N,N , N的合理设计-为计算预测的外球自由基转移途径量身定制的配体。该协议为构建手性 C( sp ³ )–C( sp / sp ² / sp ³ ) 键提供了一个实用的平台，允许方便地访问一系列在有机合成和相关领域感兴趣的具有合成挑战性的季碳结构单元领域。