近日，美国哈佛大学Eric N. Jacobsen团队报道了阴离子结合法助力对映选择性光氧化还原催化。相关论文于2025年11月20日发表在《科学》杂志上。

光氧化还原催化已成为合成化学中的一种变革性策略，通过生成高活性的自由基中间体，可实现各种有价值的化学反应。手性反阴离子与阳离子自由基中间体配对为控制各种反应性环境下的绝对立体化学提供了一种潜在通用的工具。然而，离子配对对光诱导过程效率和自由基离子对反应性的影响严重限制了可以有效参与的手性阴离子。

研究组报道了中性手性小分子氢键供体与阳离子自由基中间体的反阴离子结合，可通过离子配对和其他非共价相互作用来实现对映选择性。富电子烯烃底物在四种不同类别的环加成反应中的应用，提供了具有高达99%对映体过量的四个新立体中心的环状产物。

附：英文原文

Title: An anion-binding approach to enantioselective photoredox catalysis

Author: Petra Vojáková, Eric N. Jacobsen

Issue&Volume: 2025-11-20

Abstract: Photoredox catalysis has emerged as a transformative strategy in synthetic chemistry, enabling a wide variety of valuable chemical reactions through generation of highly reactive radical ion intermediates. Pairing chiral counteranions with cation radical intermediates provides a potentially generalizable tool for controlling absolute stereochemistry in various reactivity contexts. However, ion-pairing effects on the efficiency of photoinduced processes and the reactivity of radical ion pairs impose severe limits on the chiral anions that can be engaged effectively. In this study, we report that association of neutral chiral small-molecule hydrogen-bond donors with the counteranions of cation radical intermediates can achieve enantioselectivity through ion-pairing and other noncovalent interactions. Applications to four different classes of cycloaddition reactions of electron-rich alkene substrates provide cyclic products with up to four new stereocenters in up to 99% enantiomeric excess.

DOI: adz3362

Source: https://www.science.org/doi/10.1126/science.adz3362