金属卡宾迁移官能化研究进展

doi:10.6023/cjoc202607004

摘要/Abstract

金属卡宾与炔烃的串联反应是构建复杂有机分子的强有力工具。其中,金属卡宾在炔烃参与下发生分子内或分子间迁移,进而转化为新型卡宾中间体的“卡宾迁移(Carbene Migration)”策略,近年来受到了有机化学家的广泛关注。该过程主要通过三种特征路径实现：炔烃的卡宾-炔烃复分解(CAM)途径、经由烯基阳离子物种的金属迁移途径,以及基于环丙烯中间体原位形成与开环的迁移途径。生成的过渡态卡宾中间体继而通过经典的C—H键插入、环化或小分子插入等方式发生淬灭,从而高效实现多元环化与复杂官能团化产物的构建。尽管传统的卡宾-炔烃复分解反应已有相关报道,但得益于卡宾迁移策略在高活性卡宾的间接获取、多组分复杂环系的一步构建以及多重迁移在复杂材料分子骨架合成中的独特优势,该领域在过去十年中取得了突破性进展。本文全面总结了近十年来以卡宾迁移为核心机制的串联环化官能团化反应,深入探讨了不同催化体系下的反应机理、构效关系及应用前景,旨在为未来设计新型卡宾转化反应及功能拓宽提供理论参考与设计思路。

关键词: 金属卡宾, 炔烃, 环化反应, C—C键构建

The tandem reactions of metal carbenes with alkynes represent a powerful strategy for constructing structurally diverse and complex organic molecules. Among these, the "carbene migration" strategy—wherein a metal carbene undergoes intramolecular or intermolecular migration in the presence of an alkyne to generate a new reactive carbene intermediate—has attracted significant attention in recent years. This migratory process typically proceeds via three distinct pathways: the carbene-alkyne metathesis (CAM)-like pathway, the metal migration pathway involving alkenyl cation intermediates, and the migration mediated by the formation and subsequent ring-opening of cyclopropene intermediates. The newly generated carbene intermediates are subsequently quenched through classical pathways such as C—H insertion, cyclization, or small molecule insertion, thereby enabling efficient cascade cyclization and functionalization. Although conventional carbene-alkyne metathesis has been occasionally reviewed, the rapid evolution of carbene migration strategies has recently unlocked unique synthetic opportunities, particularly in the indirect access to highly reactive carbenes, the assembly of sophisticated polycyclic systems, and the construction of complex material molecular skeletons via iterative migrations. This review comprehensively summarizes the advances over the past decade in cascade cyclization-functionalization reactions centered on carbene migration mechanisms. We deeply discuss the reaction mechanisms, structure-activity relationships, and synthetic applications under various catalytic systems, aiming to provide inspiring insights for the future development of novel carbene transformations and their expanded utility in functional material synthesis.

Key words: metal carbenes, alkynes, cyclization reactions, C—C bond formation

引用此文

杨洋, 吕洪旭, 姜雪峰. 金属卡宾迁移官能化研究进展[J]. 有机化学, doi: 10.6023/cjoc202607004.

Yang Yang, Lv Hongxu, Jiang Xuefeng. Recent Advances in Metal-Carbene Migration Functionalization[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202607004.

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