有机化学 ›› 2021, Vol. 41 ›› Issue (5): 1957-1967.DOI: 10.6023/cjoc202103041 上一篇    下一篇

所属专题: 热点论文虚拟合集

研究论文

4-二甲胺基吡啶-硼自由基促进的缺电子烯烃区域选择性硼氢化反应

黄云帅1, 靳小慧1, 张凤莲1,*(), 汪义丰1,*()   

  1. 1 中国科学技术大学化学系 合肥 230026
  • 收稿日期:2021-03-23 修回日期:2021-04-09 发布日期:2021-04-25
  • 通讯作者: 张凤莲, 汪义丰
  • 基金资助:
    国家自然科学基金(21971226); 中央高校基本科研业务费专项资金(WK2060000017)

4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes

Yunshuai Huang1, Xiaohui Jin1, Fenglian Zhang1,*(), Yifeng Wang1,*()   

  1. 1 Department of Chemistry, University of Science and Technology of China, Hefei 230026
  • Received:2021-03-23 Revised:2021-04-09 Published:2021-04-25
  • Contact: Fenglian Zhang, Yifeng Wang
  • About author:
    * Corresponding authors. E-mail: ;
  • Supported by:
    National Natural Science Foundation of China(21971226); Fundamental Research Funds for the Central Universities(WK2060000017)

含硼有机化合物在合成化学中具有重要的应用价值, 硼氢化反应是构建有机硼化合物最常用的方法之一. 利用4-二甲氨基吡啶硼自由基与缺电子烯烃的自由基硼氢化反应, 高区域选择性地构建了α-硼取代产物. 该反应条件温和, 官能团容忍性好, 底物范围广. 多种α,β-不饱和酯、酰胺、羧酸、腈、三氟甲基化合物、砜以及磷酸酯均能顺利发生反应, 得到的含硼产物可以进一步应用于后续碳-碳键的构建.

关键词: 4-二甲氨基吡啶硼自由基, 缺电子烯烃, 区域选择性, 硼氢化反应, 自由基化学

Organoboron compounds have shown significant applications in modern chemical synthesis. Hydroboration of alkenes is among the most widely used methods to access these targets. Herein, a regioselective radical hydroboration reaction of electron-deficient alkenes with 4-dimethylaminopyridine (DMAP)-boryl radical for the synthesis of α-boryl functionalized molecules is reported. The reaction features specific α-regioselectivity, mild reaction conditions, good functional group tolerance, and broad substrate scope. α,β-Unsaturated esters, amides, carboxylic acid, nitrile, trifluoromethyl molecule, sulfone, and phosphonate are viable substrates for this reaction. The resulting α-boryl functionalized molecules can be further transformed to various useful building blocks.

Key words: 4-dimethylaminopyridine-boryl radical, electron-deficient alkenes, regioselectivity, hydroboration, radical chemistry