Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (12): 1297-1308.DOI: 10.6023/A20070294 Previous Articles     Next Articles



刘谦益a, 张雷a, 莫凡洋a,b   

  1. a 北京大学 工学院能源与资源工程系 北京 100871;
    b 江苏省东海县硅产业科技创新中心 连云港 222300
  • 投稿日期:2020-07-07 发布日期:2020-08-01
  • 通讯作者: 莫凡洋
  • 作者简介:刘谦益,北京大学工学院2017级博士生.本科毕业于北京大学工学院,博士阶段师从莫凡洋特聘研究员,主要从事有机自由基硼酯化和清洁高效有机合成方法学研究.
  • 基金资助:
    项目受国家自然科学基金(Nos.21772003 and 21933001)资助.

Organic Borylation Reactions via Radical Mechanism

Liu Qianyia, Zhang Leia, Mo Fanyanga,b   

  1. a Department of Energy and Resources Engineering, College of Engineering, Peking University, Beijing 100871, China;
    b Jiangsu Donghai Silicon Industry S&T Innovation Center, Lianyungang 222300, China
  • Received:2020-07-07 Published:2020-08-01
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21772003 and 21933001).

Organoboronic acids and esters are highly valuable building blocks in cross-coupling reactions and practical intermediates of various functional group transformations. Additionally, organoboronic acids can be utilized directly as small molecule drugs. Therefore, development of efficient methods to synthesize organoboronic compounds is of significant importance. Traditional pathways to synthesize organoboronic compounds mainly rely on electrophilic borylation of organometallic reagent and transition-metal-catalyzed borylation. Radical intermediates have unique chemical properties which are quite different from those of polar intermediates resulted from the heterolysis of chemical bonds and those of the organometallic compounds during transition metal catalysis. As such, borylation based on radical mechanism possesses distinctive reaction process, substrate scope, reaction selectivity, etc., and have great potential in synthesis of organoboronic compounds. In 2010, the Wang's group first reported borylation via a radical mechanism. This method realized an efficient direct conversion of anilines into aryl organoboronic esters. Inspired by this innovative work, more and more borylation methods via radical intermediates have been reported and developed as new avenues for C-B bond formation in the past decade. A series of studies show that organoboronic acids and esters could be efficiently constructed by the reaction of aryl/alkyl radicals with diboron compounds. In this paper, we summarize the recent development of borylation reactions via radical mechanisms, including aryl and alkyl radical borylation. As for aryl radical borylation, the activation of substrates containing C-N, C-O, C-S, C-X (X=halogen) bonds and carboxylic acids to C-B bond is summarized respectively. As for alkyl radical borylation, the activation of substrates containing C-N, C-O, C-X (X=halogen), C-C bonds and carboxylic acids to C-B bond is summarized respectively. Finally, we provide a perspective on the future development direction of this research area.

Key words: radical chemistry, borylation reaction, diboron compounds, aryl radical, alkyl radical