华中师范大学徐浩团队报道了铜-乙烯基亚乙烯中间体的远端对映选择性[4 + 1]环化反应。相关研究成果发表在2022年11月11日出版的国际学术期刊《美国化学会杂志》。

通过简洁的远程立体控制策略，首次实现了炔烯丙基酯与1,3-二羰基化合物的铜催化对映选择性[4+1]环化。通过使用新的C4合成子炔烯丙基酯中的一种新的手性铜-乙烯基亚乙烯基物种，开发了非常遥远的ε区域选择性亲核取代。因此，获得了范围广泛、化学选择性、区域选择性和对映选择性水平优异的多种螺旋环。

此外，详细的机制研究表明，炔烯丙基取代和Conia-ene级联途径对远程立体化学诱导过程有影响。

附：英文原文

Title: Remote Enantioselective [4 + 1] Annulation with Copper-Vinylvinylidene Intermediates

Author: Han-Han Kong, Cuiju Zhu, Shuang Deng, Guang Xu, Ruinan Zhao, Chaochao Yao, Hua-Ming Xiang, Chunhui Zhao, Xiaotian Qi, Hao Xu

Issue&Volume: November 11, 2022

Abstract: The first copper-catalyzed enantioselective [4 + 1] annulation of yne-allylic esters with 1,3-dicarbonyl compounds was realized through an elegant remote stereocontrol strategy. The very remote ε regioselective nucleophilic substitution was developed by employing a novel chiral copper-vinylvinylidene species from the new C4 synthon yne-allylic esters. Thus, greatly diverse spirocycles were obtained with ample scope and excellent levels of chemo-, regio-, and enantioselectivities. Moreover, detailed mechanistic studies suggest an yne-allylic substitution and Conia-ene cascade pathway on the remote stereochemical induction progress.

DOI: 10.1021/jacs.2c09572

Source: https://pubs.acs.org/doi/10.1021/jacs.2c09572