He Bin-Qing, Zhao Lu, Zhang Jun, Bao Wen-Hui, Yang Mingjun, Wu Xuesong
Hubei Key Laboratory of Bioinorganic Chemistry & Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, P.R. China.
Computational R&D, Shenzhen Jingtai Technology Co., Ltd. (XtalPi), Shenzhen, 518000, P.R. China.
Angew Chem Int Ed Engl. 2025 Jun 10;64(24):e202423795. doi: 10.1002/anie.202423795. Epub 2025 Apr 14.
The 1,3-benzodithiolylium (BDT) cation was identified as an efficient hydroxyl-activating reagent for the photocatalytic deoxygenative radical functionalization of alcohols in the absence of any electron transfer process. A series of unprecedented photocatalytic energy transfer (EnT)-driven deoxygenative radical coupling reactions of alcohols with bifunctional oxime carbonates have been developed based on the activation by BDT. Nickel-catalyzed radical sorting followed by C(sp)─C(sp) bond construction facilitates the heteroselective cross-coupling of two distinct alkyl radicals originating from parallel radical relays. These reactions allow the versatile synthesis of diverse nitrogen-containing molecules, including amino acid derivatives, imines, nitriles, and pyrrolines, by using ubiquitous alcohols as regiodefined alkyl building blocks.
1,3-苯并二硫鎓（BDT）阳离子被确定为一种有效的羟基活化试剂，用于在不存在任何电子转移过程的情况下对醇进行光催化脱氧自由基官能化。基于BDT的活化作用，开发了一系列前所未有的光催化能量转移（EnT）驱动的醇与双功能肟碳酸酯的脱氧自由基偶联反应。镍催化的自由基分类随后进行C(sp)─C(sp)键构建，促进了源自平行自由基接力的两个不同烷基自由基的杂选择性交叉偶联。这些反应通过使用普遍存在的醇作为区域定义的烷基构建单元，能够多样地合成各种含氮分子，包括氨基酸衍生物、亚胺、腈和吡咯啉。
