文献类型：期刊文献

英文题名：Catalyst-Controlled Chemodivergent Carbene Transfer Reactions With Bicyclo[1.1.0]butane-Derived Acceptor Metallocarbenes

作者：Ren, Hao-Song[1];Xie, Pei-Pei[2];Liu, Si-Wen[1];Cheng, Wei[1];Liu, Peng[2];Zheng, Jun[1]

机构：[1]East China Univ Sci & Technol, Shanghai Frontiers Sci Ctr Optogenet Tech Cell Met, Sch Pharm, State Key Lab Bioreactor Engn, Shanghai, Peoples R China;[2]Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA

年份：2026

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20261820646181);WOS:【SCI-EXPANDED(收录号:WOS:001753959100001)】；

基金：This research is supported by the National Natural Science Foundation of China (22301075), the Shanghai Scientific and Technological Innovation Projects (23ZR1417400), the Noncommunicable Chronic Diseases-National Science and Technology Major Project (2024ZD0528200), the Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, and the State Key Laboratory of Bioreactor Engineering. The authors thank the Analysis and Testing Center of East China University of Science and Technology for help with NMR and HRMS analysis. DFT calculations were carried out at the University of Pittsburgh Center for Research Computing and Data.

语种：英文

外文关键词：bicyclo[1.1.0]butanes; C(sp2)-H insertion; chemodivergent synthesis; cyclopropanation; metallocarbenes

摘要：Transition-metal-catalyzed carbene transfer reactions are powerful tools in organic synthesis, yet they traditionally rely on diazo compounds, which raise stability and safety concerns. While alternative precursors have emerged, a general, redox-neutral, and atom-economical platform for metallocarbenes generation remains a persistent challenge. Herein, we introduce carboxamide-functionalized BCBs as versatile carbene precursors that undergo catalyst-controlled chemodivergent reactions. Under nickel catalysis, cyclopropanation of multisubstituted alkenes proceeds via an acceptor-type Ni-carbene, affording azabicyclo[n.1.0] architectures bearing up to three contiguous stereocenters with excellent diastereocontrol. In contrast, copper catalysis promotes efficient and chemoselective formal C(sp2)& horbar;H insertion to access allyl oxindoles. Both protocols exhibit broad substrate scope, high functional group tolerance, and exceptional atom economy, and their synthetic utility is highlighted through the preparation of core structures of bioactive compounds. Computational and experimental studies reveal that Ni-carbene generation proceeds via a stepwise dual C & horbar;C cleavage, contrasting with the concerted dual cleavage and subsequent electrophilic aromatic substitution manifold established for the copper system.