清华大学李必杰团队报道了通过酰胺C-H裂解的铱催化α-烯烃的支选择性和对映选择性加氢烯烃化反应。相关研究成果于2022年9月19日发表于国际一流学术期刊《美国化学会杂志》。

催化原料α-烯烃支链选择性氢功能化形成对映体富集的手性化合物，是不对称催化中一种特别有吸引力但又具有挑战性的转化。

该文中，研究人员报道了铱催化的α-烯烃通过烯酰胺的定向C-H裂解的不对称氢烯基化。这种原子经济的加成过程具有高度的支链选择性和对映选择性，可提供具有烯丙基立体中心的三取代烯烃。DFT计算揭示了区域选择性和对映选择性的起源。

附：英文原文

Title: Iridium-Catalyzed Branch-Selective and Enantioselective Hydroalkenylation of α-Olefins through C–H Cleavage of Enamides

Author: Xin Sun, En-Ze Lin, Bi-Jie Li

Issue&Volume: September 19, 2022

Abstract: Catalytic branch-selective hydrofunctionalization of feedstock α-olefins to form enantioenriched chiral compounds is a particularly attractive yet challenging transformation in asymmetric catalysis. Herein we report an iridium-catalyzed asymmetric hydroalkenylation of α-olefins through directed C–H cleavage of enamides. This atom-economical addition process is highly branch-selective and enantioselective, delivering trisubstituted alkenes with an allylic stereocenter. DFT calculations reveal the origin of regio- and enantioselectivity.

DOI: 10.1021/jacs.2c07477

Source: https://pubs.acs.org/doi/10.1021/jacs.2c07477