Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (2): 458-470.DOI: 10.6023/cjoc202108027 Previous Articles     Next Articles



乐柏佟a, 吴新鑫a, 朱晨a,b,*()   

  1. a 苏州大学材料与化学化工学部 江苏省有机合成重点实验室 苏州 215123
    b 中国科学院上海有机化学研究所 天然产物有机合成重点实验室 上海 200032
  • 收稿日期:2021-08-17 修回日期:2021-10-05 发布日期:2022-02-24
  • 通讯作者: 朱晨
  • 基金资助:

Recent Advances in Vinyl Radical-Mediated Hydrogen Atom Transfer

Baitong Yuea, Xinxin Wua, Chen Zhua,b()   

  1. a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu 215123
    b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2021-08-17 Revised:2021-10-05 Published:2022-02-24
  • Contact: Chen Zhu
  • Supported by:
    National Natural Science Foundation of China(21971173)

In recent years, vinyl radical-mediated hydrogen atom transfer (HAT) has received increasing attention. This protocol provides an efficient pathway for radical cyclization and regioselective C(sp3)—H bond functionalization including vinylation, alkynylation, halogenation, arylation, etc. Generally, vinyl radicals are generated from single electron reduction of vinyl halides or the addition of extra radical to alkynes. The reaction pathways depend on substrates. For example, the resulting alkyl radical arising from vinyl radical-mediated HAT process is prone to be intramolecularly re-added to alkene, leading to cyclic products. When employing specific propargyl alcohols as substrates, the cyclic alkyl radical intermediate undergoes β-scission of C—C bond to realize vinyl migration. In addition, intermolecular radical trapping usually occurs by using internal alkynes. The transformation based on vinyl radical-mediated HAT features high regioselectivity, good atom-economy, and broad diversity of reaction modes. The recent advances in this research area are summarized.

Key words: radical reaction, C—H bond functionalization, 1,5-hydrogen atom transfer, functional group migration, vinyl radical