哈尔滨工业大学史雷团队近日通过邻苯二甲酸酯衍生的质子耦合电子转移介体实现α-亚氨基含氧酸和烷醇的光诱导开环功能化。该项研究成果发表在2025年5月12日出版的《中国化学》杂志上。

研究组开发了一种结合光氧化还原催化和邻苯二甲酸酯催化氢原子提取过程的双催化歧管，以实现各种裂解功能化反应。成功的关键是光催化产生系链可调双电子自由基阴离子（TDRA）作为质子耦合电子转移介质，实现基于极性匹配的杂原子中心自由基的形成，从而可以通过C-C β-裂解进一步控制化学空间的探索。 

这些反应具有非常广泛的底物通用性、克级合成、潜在的生物相容性和复杂分子的后期修饰，同时避免了在之前的研究中使用化学计量和通常不安全的过氧化物。机理研究支持由原位生成的催化TDRA实现的氧化还原中性自由基中继途径。

附：英文原文

Title: Photoinduced Ring-Opening Functionalization of α-Imino-Oxy Acids and Alkanols Enabled by Phthalate-Derived Proton-Coupled Electron Transfer Mediator

Author: Chao Tian, Lei Shi

Issue&Volume: 2025-05-12

Abstract: A dual catalytic manifold that combines photoredox catalysis and phthalate-catalyzed hydrogen-atom abstraction process has been developed to realize diverse fragmentation-functionalization reactions. Key to success is photocatalytic generation of tether-tunable distonic radical anions (TDRAs) as proton-coupled electron transfer mediators, enabling polarity-matching-based formation of heteroatom-centered radicals that allows for further controlled exploration of chemical space via C–C β-scission. These reactions feature exceptionally broad substrate generality, gram-scale synthesis, potential biocompatibility and late-stage modification of complex molecules, while obviating the use of stoichiometric and often unsafe peroxides in our previous studies. Mechanistic studies support a redox-neutral radical relay pathway enabled by in situ-generated, catalytic TDRAs.

DOI: 10.1002/cjoc.70074

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.70074