浙江理工大学李传莹团队报道了光解氮烯介导的无金属模块化 S–N/O–N 键构建。该项研究成果发表在2026年6月10日出版的《中国化学》杂志上。

氮烯介导的 S–H/O–H 插入反应是构建高附加值 N–S/N–O 键的核心策略，这些结构单元在药物、功能材料和农用化学品中不可或缺。然而，传统方法存在诸多难以克服的问题：严重的副反应（如Curtius 重排）、苛刻的反应条件，以及硫醇/醇的强配位作用导致过渡金属催化剂失活。

研究组报道了一种无金属光化学方法，以二苯并噻吩亚磺酰亚胺为氮烯前体，在室温下通过365 nm LED光照引发反应。简单的添加剂（2-氨基-4-氯苯甲酸）发挥双重关键作用：介导三重态能量转移以。活化亚磺酰亚胺，并作为质子供体抑制副反应。全面的机理研究（自由基捕获实验、EPR、纳秒瞬态吸收光谱和DFT计算）证实，单线态氮烯是主要路径中的关键反应中间体，而对于硫醇底物，三线态氮烯介导的自由基-自由基交叉偶联机制同样可行。该方法具有底物兼容性广、可放大合成且产率不损失、合成实用性得到验证等特点，为高效构建 N–S/N–O 键提供了实用途径。

附：英文原文

Title: Metal-Free Modular S–N/O–N Bond Construction through Photolyzed Nitrenes

Author: Hui Meng, Ye Hu, Ying-Ning Zhao, Jiamin Zhang, Ze-Feng Xu, Jialong Jie, Hongmei Su, Mingming Yu, Chuan-Ying Li

Issue&Volume: 2026-06-10

Abstract: Nitrene-mediated S–H/O–H insertion reactions serve as a core strategy for constructing value-added N–S/N–O bonds, which are indispensable motifs in pharmaceuticals, functional materials, and agrochemicals. However, traditional approaches are plagued by intractable issues: severe side reactions (e.g., Curtius rearrangement), harsh reaction conditions, and transition-metal catalyst deactivation caused by strong coordination of thiols/alcohols. Herein, we report a metal-free photochemical protocol using dibenzothiophene sulfilimines as nitrene precursors, triggered by 365 nm LED irradiation at room temperature. Simple additives (2-amino-4-chlorobenzoic acid) play dual pivotal roles: mediating triplet energy transfer to activate sulfilimines and acting as proton donors to suppress side reactions. Comprehensive mechanistic studies (radical capture experiment, EPR, nanosecond transient absorption spectroscopy, and DFT calculations) confirm singlet nitrene as the key reactive intermediate for the dominant pathway, while a triplet nitrene-mediated radical-radical cross-coupling mechanism is also feasible for thiol substrates. This protocol features broad substrate compatibility, scalable synthesis without yield loss, and validated synthetic utility, providing a practical avenue for efficient N–S/N–O bond formation.

DOI: 10.1002/cjoc.70645

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70645