The hydroalkylation reaction of olefins with alkanes is a highly desirable synthetic transformation toward the construction of C(sp 3 )─C(sp 3 ) bonds. However, such transformation has proven to be challenging for unactivated olefins, particularly when the substrates lack directing groups or acidic C(sp 3 )─H bonds. Here, we address this challenge by merging NiH-catalyzed radical relay strategy with a HAT (hydrogen atom transfer) process. In this catalytic system, a nucleophilic alkyl radical is generated from a C(sp 3 )─H compound in the presence of a HAT promotor, which couples with an alkyl metallic intermediate generated from the olefin substrate with a NiH catalyst to form the C(sp 3 )─C(sp 3 ) bond. Starting from easily available materials, the reaction not only demonstrates wide functional group compatibility but also provides hydroalkylation products with regiodivergence and excellent enantioselectivity through effective catalyst control under mild conditions.

中文翻译：

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通过 NiH 催化的自由基传递实现未活化烯烃与 C（sp 3 ）─H 化合物的加氢烷基化反应


烯烃与烷烃的加氢烷基化反应是朝着构建 C（sp 3 ）─C（sp 3 ） 键的方向发展的一种非常理想的合成转化。然而，这种转变已被证明对未活化的烯烃具有挑战性，特别是当底物缺乏定向基团或酸性 C（sp 3 ）─H 键时。在这里，我们通过将 NiH 催化的自由基中继策略与 HAT（氢原子转移）过程相结合来应对这一挑战。在该催化系统中，在 HAT 启动子存在下，由 C（sp 3 ）─H 化合物生成亲核烷基自由基，该化合物与烯烃底物生成的烷基金属中间体与 NiH 催化剂偶联，形成 C（sp 3 ）─C（sp 3 ） 键。该反应从容易获得的材料开始，不仅表现出广泛的官能团相容性，而且通过在温和条件下通过有效的催化剂控制提供具有区域分歧和出色对映选择性的氢烷基化产物。