Silanes are used as a simple and common hydride source owing to their chemical stability, neat and easy-to-handle nature and advantage of generally not requiring any precautions during their activation via nickel catalysis. Due to their hydride donor nature, upon reaction with a ligand-tailored nickel complex, they generate reactive Ni–H species, which are normally more prone to facile addition to the π-bond, resulting in an organonickel intermediate, which can undergo various sequential cross-coupling reactions. Notably, recent developments have brought π-hydrofunctionalization reactions facilitated by Ni–H catalysis to the forefront. In addition, the use of suitable chiral ligands has paved the way for the realization of asymmetric hydrofunctionalization reactions in the realm of π-bonds. This review aims to provide an in-depth analysis of the latest advancements in C–C and C–heteroatom bond formation via silane-mediated hydrofunctionalization catalyzed by nickel hydride. In particular, the NiH/ligand-catalytic system exhibits remarkable reactivity with π-substrates, including alkenes, alkynes, and allenes. A thorough mechanistic understanding of these processes offers insights into the trends and future directions to drive innovation in catalyst design, fine tune reaction systems, and develop new cross-coupling reactions with π-substrates.

中文翻译：

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硅烷作为 Ni-H 催化的多功能氢化物源：π-氢功能化的有前途的工具


硅烷因其化学稳定性、纯净且易于处理的性质以及在镍催化活化过程中通常不需要任何预防措施的优点而被用作简单且常见的氢化物源。由于它们的氢化物供体性质，在与配体定制的镍配合物反应时，它们会生成反应性 Ni-H 物质，这些物质通常更容易加成到 π 键上，从而产生有机镍中间体，该中间体可以经历各种顺序反应交叉偶联反应。值得注意的是，最近的发展将 Ni-H 催化促进的 π-氢官能化反应带到了前沿。此外，合适的手性配体的使用为π键领域不对称氢官能化反应的实现铺平了道路。本综述旨在深入分析通过氢化镍催化的硅烷介导的氢官能化形成 C-C 和 C-杂原子键的最新进展。特别是，NiH/配体催化系统与π底物（包括烯烃、炔烃和丙二烯）表现出显着的反应活性。对这些过程的透彻理解可以帮助我们深入了解趋势和未来方向，从而推动催化剂设计创新、微调反应系统以及开发新型 π 底物交叉偶联反应。