Selective construction of two distinct alkyl–alkyl bonds across the C=C bond of simple unactivated olefins is a persistent challenge in organic synthesis. Transition metal-catalysed alkene-dicarbofunctionalization reactions proceeding via classic organometallic elementary reaction mechanism (oxidative addition/transmetalation/reductive elimination) suffered from non-bond forming side reactivities of alkyl–metal intermediates (facile β-hydride elimination) and thus strongly limited the substrate scope of olefins and coupling reagents. Here we demonstrate that the problem of alkyl–metal side reactivities can be overcome with an electron-shuttle catalysis approach, wherein the metal catalyst acts as an electron shuttle to induce and quench the radical intermediates and facilitate the alkyl–alkyl bond formation via radical-unsaturated bond addition. This strategy was applied to a modular alkylative aminomethylation of olefins with two distinct alkyl–alkyl bonds generated through nickel electron-shuttle catalysis. Mechanistic studies supported the formation of carbon-centred radical species and the involvement of radical addition processes.

在简单未活化烯烃的 C=C 键上选择性构建两个不同的烷基-烷基键是有机合成中持续存在的挑战。通过经典有机金属基元反应机制（氧化加成/金属转移/还原消除）进行的过渡金属催化的烯烃二碳官能化反应受到烷基金属中间体的非成键副反应性（容易的β-氢化物消除）的影响，因此强烈限制了底物烯烃和偶联剂的范围。在这里，我们证明了烷基-金属副反应性的问题可以通过电子穿梭催化方法来克服，其中金属催化剂充当电子穿梭来诱导和猝灭自由基中间体并通过自由基促进烷基-烷基键的形成。不饱和键加成。该策略应用于具有通过镍电子穿梭催化产生的两个不同烷基-烷基键的烯烃的模块化烷基化氨甲基化。机理研究支持以碳为中心的自由基物种的形成以及自由基加成过程的参与。