Department of Chemical Sciences, National Institute of Pharmaceutical Education and Research (NIPER), Hyderabad, 500 037, Telangana, India.
Chem Asian J. 2021 Mar 1;16(5):443-459. doi: 10.1002/asia.202001219. Epub 2021 Feb 4.
Metal carbenes play a pivotal role in transition-metal-catalyzed synthetic transfer reactions. The metal carbene is generated either from a diazo compound through facile extrusion of N with a metal catalyst or in situ generated from other sources like triazoles, pyriodotriazoles, sulfoxonium ylides and iodonium-ylide. On the other hand, Co(III), Rh(III) & Ir(III)-catalyzed C-H functionalizations have been well established as a key synthetic step to enable the construction of various synthetic transformations. Interestingly, in recent years, merging of these two concepts C-H activation and carbene migratory insertion gained much attention, in particular group 9 metal-catalyzed arene C-H functionalizations with carbene precursors via carbene migratory insertion. In this review, we summarize recent advances in Co(III), Rh(III) & Ir(III)-catalyzed direct C-H alkylation/alkenylation/arylation with carbene precursors and also discuss key synthetic intermediates within the catalytic cycles.
金属卡宾在过渡金属催化的合成转移反应中起着关键作用。金属卡宾可以通过金属催化剂容易地将 N 从重氮化合物中挤出而产生，也可以从其他来源（如三唑、吡咯并三唑、亚磺酰亚胺叶立德和碘鎓叶立德）原位生成。另一方面，Co(III)、Rh(III) 和 Ir(III) 催化的 C-H 官能化已被确立为关键的合成步骤，以实现各种合成转化的构建。有趣的是，近年来，这两个概念——C-H 活化和卡宾迁移插入的融合引起了极大的关注，特别是第 9 族金属催化的芳基 C-H 官能化，通过卡宾迁移插入使用卡宾前体。在这篇综述中，我们总结了 Co(III)、Rh(III) 和 Ir(III) 催化的直接 C-H 烷基化/烯基化/芳基化反应的最新进展，并讨论了催化循环中的关键合成中间体。
