Zhong Ping-Fu, Tu Jia-Lin, Zhao Yating, Zhong Nan, Yang Chao, Guo Lin, Xia Wujiong
State Key Lab of Urban Water Resource and Environment, Harbin Institute of Technology (Shenzhen), Shenzhen, 518055, China.
College of Chemical and Material Engineering, Quzhou University, Quzhou, 324000, China.
Nat Commun. 2023 Oct 16;14(1):6530. doi: 10.1038/s41467-023-42264-9.
Organoboron compounds are of high significance in organic synthesis due to the unique versatility of boryl substituents to access further modifications. The high demand for the incorporation of boryl moieties into molecular structures has witnessed significant progress, particularly in the C(sp)-H borylation of hydrocarbons. Taking advantage of special characteristics of photo/electrochemistry, we herein describe the development of an oxidative C(sp)-H borylation reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. The reaction exhibits broad substrate scope (>57 examples), and includes the use of simple alkanes, halides, silanes, ketones, esters and nitriles as viable substrates. Notably, unconventional regioselectivity of C(sp)-H borylation is achieved, with the coupling site of C(sp)-H borylation selectively located in the distal methyl group. Our method is operationally simple and easily scalable, and offers a feasible approach for the one-step synthesis of high-value organoboron building blocks from simple hydrocarbons, which would provide ample opportunities for drug discovery.
有机硼化合物在有机合成中具有重要意义，这是因为硼基取代基具有独特的多功能性，能够进行进一步修饰。将硼基部分引入分子结构的高需求见证了显著进展，特别是在烃类的C(sp)-H硼化反应中。利用光/电化学的特殊特性，我们在此描述了一种在无金属和无氧化剂条件下通过光电化学策略实现的氧化C(sp)-H硼化反应的发展。该反应具有广泛的底物范围（>57个实例），并且包括使用简单的烷烃、卤化物、硅烷、酮、酯和腈作为可行的底物。值得注意的是，实现了C(sp)-H硼化反应的非常规区域选择性，C(sp)-H硼化反应的偶联位点选择性地位于远端甲基中。我们的方法操作简单且易于放大，为从简单烃类一步合成高价值有机硼结构单元提供了一种可行的方法，这将为药物发现提供充足的机会。
