近日，华中师范大学肖文精团队报道了手性布朗斯特酸催化不对称光烯醇化/狄尔斯-阿尔德反应。这一研究成果发表在2026年1月27日出版的《科学通报》杂志上。

光烯醇化/狄尔斯-阿尔德反应已成为现代合成化学中构建苯并稠合碳环骨架的重要策略。然而，光诱导中间体的高反应活性通常需要亚化学计量的手性催化剂才能实现充分的对映体控制，这限制了催化不对称光烯醇化/狄尔斯-阿尔德反应的发展。

研究组报道了一种在温和条件下进行的手性布朗斯特酸催化不对称光烯醇化/狄尔斯-阿尔德反应，通过稳定瞬态光烯醇中间体，实现了芳基酮与乙烯基氮杂芳烃的高对映选择性[4+2]环加成反应。该策略能够直接以良好收率和优异对映选择性（最高达97%收率，>19:1 dr，>99% ee）获得含氮杂芳烃的手性碳环加成产物及具有吸引力的高对映体纯度螺环内酯类化合物。值得注意的是，对照实验与机理研究表明，手性布朗斯特酸独特的多功能活化作用对于实现高反应活性和对映体控制至关重要。

附：英文原文

Title: Enantioselective photoenolization/Diels–Alder reaction catalyzed by chiral Brnsted acid

Author: Ying Cheng a b, Wen-Jing Xiao a b c

Issue&Volume: 2026/01/27

Abstract: Photoenolization/Diels–Alder (PEDA) reaction has emerged as a promising strategy for constructing benzannulated carbocyclic frameworks in modern synthetic chemistry. However, the high reactivity of photoinduced intermediates typically necessitates a substoichiometric amount of chiral catalyst for sufficient enantiocontrol, thereby limiting the development of catalytic asymmetric PEDA reaction. Herein, we report a chiral Brnsted acid-catalyzed asymmetric PEDA reaction under mild conditions, which achieves highly enantioselective [4+2] cycloaddition of aryl ketones with vinylazaarenes by stabilizing transient photoenol intermediates. This strategy enables straightforward access to azaarene-containing chiral carbocyclic adducts and attractive enantioenriched spiro lactones in good yields with excellent enantioselectivity (up to 97% yield, >19:1 dr, >99% ee). Notably, control experiments and mechanism studies indicate that unique multifunctional activation of chiral Brnsted acids is crucial for achieving high reactivity and enantiocontrol.

DOI: 10.1016/j.scib.2026.01.059

Source: https://www.sciencedirect.com/science/article/abs/pii/S209592732600085X