Carbon–carbon bonds, including those between sp3-hybridized carbon atoms (alkyl–alkyl bonds), typically comprise much of the framework of organic molecules. In the case of sp3-hybridized carbon, the carbon can be stereogenic and the particular stereochemistry can have implications for structure and function1–3. As a consequence, the development of methods that simultaneously construct alkyl–alkyl bonds and control stereochemistry is important, although challenging. Here we describe a strategy for enantioselective alkyl–alkyl bond formation, in which a racemic alkyl electrophile is coupled with an olefin in the presence of a hydrosilane, rather than via a traditional electrophile–nucleophile cross-coupling, through the action of a chiral nickel catalyst. We demonstrate that families of racemic alkyl halides—including secondary and tertiary electrophiles, which have not previously been shown to be suitable for enantioconvergent coupling with alkyl metal nucleophiles—cross-couple with olefins with good enantioselectivity and yield under very mild reaction conditions. Given the ready availability of olefins, our approach opens the door to developing more general methods for enantioconvergent alkyl–alkyl coupling.Nickel-catalysed coupling of racemic alkyl electrophiles and olefins in the presence of a hydrosilane is achieved with good enantioselectivity and yield under very mild reaction conditions.

中文翻译：

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二级和三级亲电试剂与烯烃的催化对映会聚偶联

碳 - 碳键，包括 sp3 杂化碳原子（烷基 - 烷基键）之间的那些，通常构成有机分子的大部分框架。在 sp3 杂化碳的情况下，碳可以是立体的，特定的立体化学会对结构和功能产生影响 1-3。因此，开发同时构建烷基-烷基键和控制立体化学的方法很重要，尽管具有挑战性。在这里，我们描述了一种形成对映选择性烷基 - 烷基键的策略，其中外消旋烷基亲电试剂在氢硅烷存在下与烯烃偶联，而不是通过传统的亲电试剂 - 亲核试剂交叉偶联，通过手性镍的作用催化剂。我们证明了外消旋烷基卤化物家族 - 包括二级和三级亲电试剂，它​​们之前没有被证明适合与烷基金属亲核试剂对映会聚偶联 - 在非常温和的反应条件下与烯烃交叉偶联，具有良好的对映选择性和产率。鉴于烯烃随时可用，我们的方法为开发更通用的烷基-烷基对映聚合方法打开了大门。在氢硅烷存在下，外消旋烷基亲电试剂和烯烃的镍催化偶联在非常温和的条件下以良好的对映选择性和产率实现反应条件。以前没有被证明适用于与烷基金属亲核试剂的对映会聚偶联——与烯烃交叉偶联，在非常温和的反应条件下具有良好的对映选择性和产率。鉴于烯烃随时可用，我们的方法为开发更通用的烷基-烷基对映聚合方法打开了大门。在氢硅烷存在下，外消旋烷基亲电试剂和烯烃的镍催化偶联在非常温和的条件下以良好的对映选择性和产率实现反应条件。以前没有被证明适合与烷基金属亲核试剂对映会聚偶联——与烯烃交叉偶联，在非常温和的反应条件下具有良好的对映选择性和产率。鉴于烯烃随时可用，我们的方法为开发更通用的烷基-烷基对映聚合方法打开了大门。在氢硅烷存在下，外消旋烷基亲电试剂和烯烃的镍催化偶联在非常温和的条件下以良好的对映选择性和产率实现反应条件。