After decades of palladium dominating the realm of transition-metal-catalyzed cross-coupling, recent years have witnessed exciting advances in the development of new nickel-catalyzed cross-coupling reactions to form C(sp³) centers. Nickel possesses distinct properties compared with palladium, such as facile single-electron transfer to C(sp³) electrophiles and rapid C–C reductive elimination from Ni^III. These properties, among others, make nickel particularly well-suited for reductive cross-coupling (RCC) in which two electrophiles are coupled and an exogenous reductant is used to turn over the metal catalyst. Ni-catalyzed RCCs use readily available and stable electrophiles as starting materials and exhibit good functional group tolerance, which makes them appealing for applications in the synthesis of complex molecules. Building upon the foundational work in Ni-catalyzed RCCs by the groups of Kumada, Durandetti, Weix, and others, as well as the advancements in Ni-catalyzed enantioselective redox-neutral cross-couplings led by Fu and co-workers, we initiated a program to explore the feasibility of developing highly enantioselective Ni-catalyzed RCCs. Our research has also been driven by a keen interest in unraveling the factors contributing to enantioinduction and electrophile activation as we seek new avenues for advancing our understanding and further developing these reactions.

中文翻译：

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Ni 催化对映选择性 C(sp2)–C(sp3) 键构建

几十年来，钯在过渡金属催化交叉偶联领域占据主导地位，近年来，在形成 C(sp ³ ) 中心的新型镍催化交叉偶联反应的开发方面取得了令人兴奋的进展。与钯相比，镍具有独特的特性，例如易于单电子转移至 C(sp ^{3 ) 亲电子试剂以及从 Ni III}中快速进行 C-C 还原消除。除其他外，这些特性使镍特别适合还原交叉偶联（RCC），其中两种亲电子试剂偶联，并使用外源还原剂来翻转金属催化剂。镍催化的 RCC 使用易于获得且稳定的亲电子试剂作为起始材料，并表现出良好的官能团耐受性，这使得它们在复杂分子的合成中具有吸引力。基于 Kumada、Durandetti、Weix 等小组在 Ni 催化 RCC 方面的基础工作，以及 Fu 及其同事领导的 Ni 催化对映选择性氧化还原中性交叉偶联方面的进展，我们发起了一项该计划旨在探索开发高对映选择性镍催化 RCC 的可行性。我们的研究也受到了对揭示对映诱导和亲电试剂激活的影响因素的浓厚兴趣所推动，因为我们寻求新的途径来增进我们的理解并进一步发展这些反应。