Zhu Congjun, Dong Jie, Liu Xueting, Gao Liuzhou, Zhao Yue, Xie Jin, Li Shuhua, Zhu Chengjian
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Angew Chem Int Ed Engl. 2020 Jul 27;59(31):12817-12821. doi: 10.1002/anie.202005749. Epub 2020 May 20.
In this Communication, we report an unprecedented β-regioselective radical inverse hydroboration (compared with ionic hydroboration) of α,β-unsaturated amides with NHC-BH enabled by photoredox catalysis. Density functional theory (DFT) calculations show that the unique photoredox cycle is a key factor to control the β-regioselective radical hydroboration, by lowering the energy barrier in comparison with other pathways. This protocol provides a general and convenient route to construct a wide range of structurally diverse β-borylated amides in synthetically useful yields under mild conditions.
在本通讯中，我们报道了一种前所未有的β-区域选择性自由基反式硼氢化反应（与离子硼氢化反应相比），该反应通过光氧化还原催化实现了α,β-不饱和酰胺与NHC-BH的反应。密度泛函理论（DFT）计算表明，独特的光氧化还原循环是控制β-区域选择性自由基硼氢化反应的关键因素，与其他途径相比，它降低了能垒。该方法提供了一条通用且便捷的途径，可在温和条件下以合成有用的产率构建多种结构多样的β-硼化酰胺。
