The development of efficient methods, particularly catalytic and enantioselective processes, for the construction of all-carbon quaternary stereocentres is an important (and difficult) challenge in organic synthesis due to the occurrence of this motif in a range of bioactive molecules. One conceptually straightforward and potentially versatile approach is the catalytic enantioconvergent substitution reaction of a readily available racemic tertiary alkyl electrophile by an organometallic nucleophile; however, examples of such processes are rare. Here we demonstrate that a nickel-based chiral catalyst achieves enantioconvergent couplings of a variety of tertiary electrophiles (cyclic and acyclic α-halocarbonyl compounds) with alkenylmetal nucleophiles to form quaternary stereocentres with good yield and enantioselectivity under mild conditions in the presence of a range of functional groups. These couplings, which probably proceed via a radical pathway, provide access to an array of useful families of organic compounds, including intermediates in the total synthesis of two natural products, (–)-eburnamonine and madindoline A.

由于该基序在一系列生物活性分子中的出现，开发用于构建全碳四元立体中心的有效方法，特别是催化和对映选择性过程是有机合成中的一个重要（也是困难）挑战。一种概念上简单且可能具有通用性的方法是有机金属亲核试剂与容易获得的外消旋叔烷基亲电试剂的催化对映收敛取代反应。然而，这种过程的例子很少见。在这里，我们证明镍基手性催化剂实现了多种叔亲电子试剂（环状和无环 α-卤代羰基化合物）与烯基金属亲核试剂的对映收敛偶联，在温和条件下，在一系列官能团。这些可能通过自由基途径进行的偶联提供了获得一系列有用的有机化合物家族的途径，包括两种天然产物 (-)-eburnamonine 和 madindoline A 的全合成中间体。