Department of Chemistry, National University of Singapore, 4 Science Drive 2, Singapore, 117544, Republic of Singapore.
Chem Soc Rev. 2023 May 9;52(9):2946-2991. doi: 10.1039/d2cs00972b.
Alkene functionalisation is a powerful strategy that has enabled access to a wide array of compounds including valuable pharmaceuticals and agrochemicals. The reactivity of the alkene π-bond has allowed incorporation of a diverse range of atoms and functional groups through a wide variety of reaction pathways. N-Heterocyclic carbenes (NHCs) are a class of persistent carbenes that are widely employed as ancillary ligands due to their ability to act as strong σ-donors compared to widely-applied conventional phosphine-based ligands. NHCs are also unique as their molecular bulk provides steric influence for regio- and stereo-control in many alkene functionalisation reactions, illustrated by the examples covered in this review. A combination of the unique reactivity of NHC ligands and nickel's characteristics has facilitated the design of reaction pathways that show distinct selectivity and reactivity, including the activation of bonds previously considered "inert", such as C-H bonds, the C-O bond of ethers and esters, and the C-N bonds of amides. This review summarises the advancements in Ni(NHC) catalysed alkene functionalisation up to 2022, covering the following major reaction classes: Heck-type reactions, hydrofunctionalisation and dicarbofunctionalisation.
烯烃官能化是一种强大的策略，它使人们能够获得包括有价值的药物和农用化学品在内的广泛化合物。烯烃π键的反应性允许通过各种各样的反应途径引入各种原子和官能团。氮杂环卡宾（NHCs）是一类持久的卡宾，由于其作为强σ供体的能力，与广泛应用的传统膦基配体相比，它们被广泛用作辅助配体。NHCs 的独特之处在于，它们的分子体积为许多烯烃官能化反应中的区域和立体控制提供了空间影响，这在本综述中涵盖的例子中得到了说明。NHC 配体的独特反应性和镍的特性的结合促进了反应途径的设计，这些反应途径表现出明显的选择性和反应性，包括以前被认为“惰性”的键的活化，如 C-H 键、醚和酯的 C-O 键以及酰胺的 C-N 键。本综述总结了截至 2022 年镍（NHC）催化的烯烃官能化的进展，涵盖了以下主要反应类别：Heck 型反应、氢官能化和二碳官能化。
