Transition Metal‐Catalyzed Carbene Coupling Reaction

作者：Ying Li, Ze Li, shufeng chen, Jian Wang · 发表于：Chinese Journal of Chemistry · 年份：2026 · DOI：10.1002/cjoc.70463 · 被引用次数：11 · 研究领域：Cyclopropane Reaction Mechanisms、Catalytic C–H Functionalization Methods、Click Chemistry and Applications

Comprehensive Summary Transition‐metal‐catalyzed carbene transfer reactions have emerged as a robust and versatile strategy in organic synthesis. Conventional carbene transfer processes primarily encompass C–H bond insertion, cyclopropanation, and ylide formation, which have found extensive applications both in academic research and industrial settings. A prominent example includes the Rh(II)‐catalyzed intramolecular N–H insertion employed in the synthesis of β‐lactam antibiotics such as thienamycin, as well as asymmetric cyclopropanation utilized in the production of chrysanthemate‐based insecticides. Over the past decade, a novel class of transition‐metal‐catalyzed transformations involving carbene precursors has gained significant attention. In these reactions, diazo compounds—or their precursors such as N ‐tosylhydrazones—serve as cross‐coupling partners for the construction of C–C single or C=C double bonds. The transformations developed thus far in this field are summarized in the accompanying figure. These processes typically proceed via metal–carbene intermediates followed by migratory insertion steps, enabling efficient bond formation under either redox‐neutral or oxidative conditions. The broad compatibility of various carbene precursors and coupling partners has greatly enhanced the synthetic utility of this approach. This carbene‐based coupling strategy has demonstrated wide applicability, with numerous transition metals—including Pd, Cu, Rh, Ni, Co, and Ir—provin...