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

作者:Kong, Han-Han; Zhu, Cuiju; Deng, Shuang; Xu, Guang; Zhao, Ruinan; Yao, Chaochao; Xiang, Hua-Ming; Zhao, Chunhui; Qi, Xiaotian*; Xu, Hao*
来源:Journal of the American Chemical Society, 2022, 144(46): 21347-21355.
DOI:10.1021/jacs.2c09572

摘要

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 epsilon 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.

  • 单位
    武汉大学