The Michaelis–Becker reaction of H-phosphonates with alkyl halides represents an ideal means for synthesizing alkyl phosphorous compounds. However, the enantioconvergent conversion of racemic alkyl halides into α-chiral alkyl phosphorous compounds in this reaction is an insurmountable challenge because of the inherent S_N2 mechanism. Here we disclose a copper-catalysed enantioconvergent radical Michaelis–Becker-type C(sp³)–P cross-coupling. Key to the success of this reaction is the use of multidentate chiral anionic ligands for enhancing the reducing capability of the copper catalyst to favour a stereoablative radical pathway over a stereospecific S_N2-type process. Moreover, the ligand architecture is also able to assist the robust association of copper species with alkyl radicals over H-phosphonates, therefore exerting remarkable chemo- and enantioselectivity. This protocol covers a range of (hetero)benzyl-, propargyl- and α-aminocarbonyl alkyl bromides and chlorides. When allied with follow-up transformations, this method provides a versatile platform for valuable α-chiral alkyl phosphorous building blocks and drug leads.

H-膦酸酯与烷基卤化物的米氏-贝克尔反应是合成烷基磷化合物的理想方法。然而，由于固有的S _N 2 机理，在该反应中将外消旋烷基卤化物对映体转化为α-手性烷基磷化合物是一个难以克服的挑战。在这里，我们公开了一种铜催化的对映会聚自由基米氏-贝克尔型 C( sp ³ )-P 交叉偶联。该反应成功的关键是使用多齿手性阴离子配体来增强铜催化剂的还原能力，从而有利于立体消除自由基途径而不是立体特异性 S _N2型工艺。此外，配体结构还能够帮助铜物种与烷基自由基在 H-膦酸盐上的稳健结合，因此发挥显着的化学和对映选择性。该协议涵盖一系列（杂）苄基-、炔丙基-和α-氨基羰基烷基溴化物和氯化物。当与后续转化相结合时，该方法为有价值的 α-手性烷基磷结构单元和药物先导物提供了一个多功能平台。