南开大学周其林团队的一项最新研究探明了配体激活铱催化α-烯烃和苯乙烯与丙烯酰胺的对映选择性氢烯化反应。相关论文于2025年4月1日发表于国际顶尖学术期刊《美国化学会杂志》上。

研制了一种新型手性二亚磷酸酯螺体配体。利用这些配体，铱催化α-烯烃和苯乙烯与丙烯酰胺实现了高度对映选择性的氢烯化反应。本文成功地将多种脂肪烯烃和芳烃与丙烯酰胺偶联制备了γ-取代手性丙烯酰胺。该反应具有支链选择性好、对映体选择性高、底物范围广、官能团耐受性好等特点。DFT计算表明，配体中的甲基在控制反应的区域选择性和对映选择性方面起着至关重要的作用。

附：英文原文

Title: Ligand Enabled Iridium-Catalyzed Enantioselective Hydroalkenylation of α-Olefins and Styrenes with Acrylamides

Author: Kai Wang, Kai-Yuan Tian, Xin-Ning Wang, Jing-Hao Chen, Chao Fan, Qi-Lin Zhou

Issue&Volume: April 1, 2025

Abstract: A new type of chiral spiro diphosphite ligand has been developed. Using these ligands, iridium-catalyzed highly enantioselective hydroalkenylation of α-olefins and styrenes with acrylamides has been realized. A variety of aliphatic and aromatic alkenes were successfully coupled with acrylamides to produce γ-substituted chiral acrylamides. The reaction exhibits excellent branched selectivity and high enantioselectivity along with broad substrate scope and good functional group tolerance. DFT calculations indicate that the methyl groups in the ligand play a crucial role in controlling both regioselectivity and enantioselectivity of the reaction.

DOI: 10.1021/jacs.4c18412

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c18412