Zhang Chenhao, Jiang Zhiyong
School of Chemical Science and Technology, Yunnan University, Kunming, Yunnan, 650500, P. R. China.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007, P. R. China.
Chem Commun (Camb). 2025 May 22;61(43):7737-7750. doi: 10.1039/d4cc06530a.
Enantioselective protonation represents a direct and effective method for constructing tertiary carbon stereocenters, which are prevalent in natural products and bioactive compounds. However, achieving catalytic asymmetric protonation has long posed challenges due to difficulties in controlling stereoselectivity. The small size of protons and their rapid transfer rates complicate the selective delivery to active intermediates, resulting in convoluted reaction pathways and pronounced background reactions. In recent years, light-driven photocatalysis has emerged as a powerful strategy in asymmetric protonation reactions, significantly broadening the range of reaction pathways and substrate types. In this review, we highlight recent advancements in this area, focusing on photoinduced single-electron transfer and energy transfer processes, where photosensitizers generate reactive intermediates for asymmetric protonation. This approach not only expands the scope of asymmetric catalysis but also presents new opportunities for green and sustainable chemistry, effectively addressing critical challenges in the construction of complex molecules.
对映选择性质子化是构建叔碳立体中心的一种直接有效的方法，叔碳立体中心在天然产物和生物活性化合物中普遍存在。然而，由于难以控制立体选择性，实现催化不对称质子化长期以来一直面临挑战。质子体积小且转移速率快，使得选择性传递至活性中间体变得复杂，导致反应路径错综复杂且背景反应明显。近年来，光驱动光催化已成为不对称质子化反应中的一种强大策略，显著拓宽了反应路径和底物类型的范围。在本综述中，我们重点介绍了该领域的最新进展，聚焦于光诱导单电子转移和能量转移过程，其中光敏剂产生用于不对称质子化的活性中间体。这种方法不仅扩大了不对称催化的范围，还为绿色和可持续化学带来了新机遇，有效应对了复杂分子构建中的关键挑战。
