Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Angew Chem Int Ed Engl. 2020 Apr 20;59(17):6750-6755. doi: 10.1002/anie.201916014. Epub 2020 Mar 2.
Migratory functionalization of alkenes has emerged as a powerful strategy to achieve functionalization at a distal position to the original reactive site on a hydrocarbon chain. However, an analogous protocol for alkyne substrates is yet to be developed. Herein, a base and cobalt relay catalytic process for the selective synthesis of (Z)-2-alkenes and conjugated E alkenes by migratory hydrogenation of terminal alkynes is disclosed. Mechanistic studies support a relay catalytic process involving a sequential base-catalyzed isomerization of terminal alkynes and cobalt-catalyzed hydrogenation of either 2-alkynes or conjugated diene intermediates. Notably, this practical non-noble metal catalytic system enables efficient control of the chemo-, regio-, and stereoselectivity of this transformation.
烯烃的迁移官能团化已成为在碳链原始反应位点的远端位置实现官能化的有效策略。然而，对于炔烃底物，仍然需要开发类似的方法。在此，本文报道了一种通过末端炔烃的迁移氢化来选择性合成（Z）-2-烯烃和共轭 E-烯烃的碱和钴接力催化过程。机理研究支持涉及末端炔烃的顺序碱催化异构化和 2-炔烃或共轭二烯中间体的钴催化氢化的接力催化过程。值得注意的是，这种实用的非贵金属催化体系能够有效地控制该转化的化学、区域和立体选择性。
