近日，南开大学叶萌春团队研究了镍铝双金属催化环丙基酮与炔在温和条件下的环加成反应。2025年12月11日出版的《美国化学会志》发表了这项成果。

过渡金属催化的环丙基酮与π-不饱和化合物间的对映选择性分子间环加成反应，是环丙烷不对称C–C键活化领域中一个长期存在的挑战。现有策略多依赖于对底物进行修饰以抑制外消旋化或稳定自由基中间体。相比之下，针对通用环丙基酮、由过渡金属催化剂主导的高效方法仍是一项难以实现的挑战。

研究组报道了一种高活性的手性二胺-氧化膦配位的Ni–Al双金属催化剂，该催化剂可在温和条件下促进对映选择性C–C环加成反应。该体系能有效抑制产物外消旋化，并以高达99%的产率和99%的对映异构体过量值（ee），提供了一系列带有α-手性叔碳中心的环戊基酮类化合物。

附：英文原文

Title: Enantioselective Ni–Al Bimetal-Catalyzed Cycloaddition of Cyclopropyl Ketones with Alkynes under Mild Conditions

Author: Yinpeng Wang, Yi Li, Haorui Wang, Lujie Ji, Yu Fu, Xingzhong Gao, Qi-Lin Zhou, Weiwei Xu, Mengchun Ye

Issue&Volume: December 11, 2025

Abstract: Transition metal-catalyzed enantioselective intermolecular cycloaddition of cyclopropyl ketones and π-unsaturated compounds represents a long-standing challenge in the asymmetric C–C bond activation of cyclopropanes. Developed strategies rely on substrate modifications to mitigate racemization or to stabilize radical intermediates. In contrast, an efficient approach governed by transition-metal catalysts for general cyclopropyl ketones remains an elusive challenge. Herein, we report a highly active chiral diamine–phosphine oxide-ligated Ni–Al bimetallic catalyst that promotes enantioselective C–C cycloaddition under mild conditions. This system effectively suppresses product racemization and affords a diverse range of cyclopentyl ketones bearing a chiral α-tertiary carbon center in up to 99% yield and 99% ee.

DOI: 10.1021/jacs.5c18087

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c18087