Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (6): 2408-2416.DOI: 10.6023/cjoc202101042 Previous Articles     Next Articles

ARTICLES

叔丁基自由基引发的1,2-炔基迁移反应研究

张萍a,c, 张天舒a, 蔡佩君a,*(), 姜波b, 屠树江b,*()   

  1. a 中国矿业大学化工学院 江苏徐州 221116
    b 江苏师范大学化学与材料科学学院 江苏徐州 221116
    c 江苏省徐州医药高等职业学校 江苏徐州 221116
  • 收稿日期:2021-01-26 修回日期:2021-02-12 发布日期:2021-02-26
  • 通讯作者: 蔡佩君, 屠树江
  • 基金资助:
    中央高校基本科研专项资金基金(JH180263)

Study on tert-Butyl Radical-Initiated 1,2-Alkynyl Migration

Ping Zhanga,c, Tianshu Zhanga, Peijun Caia(), Bo Jiangb, Shujiang Tub()   

  1. a School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou, Jiangsu 221116
    b School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116
    c Jiangsu Provincial Xuzhou Pharmaceutical Vocational College, Xuzhou, Jiangsu 221116
  • Received:2021-01-26 Revised:2021-02-12 Published:2021-02-26
  • Contact: Peijun Cai, Shujiang Tu
  • Supported by:
    Fundamental Research Funds for the Central Universities(JH180263)

A new tert-butyl radical-induced 1,2-alkynyl migration reaction is reported. By using the characteristics of in-situ-generation of tert-butyl radical from pivalaldehyde mediated by di-tert-butyl peroxide (DTBP), tert-butyl radical-triggered addition and alkynyl migration of the preformed 1,4-enynes led to the synthesis of a series of α-alkynyl ketones with good to excellent yields, thereby realizing alkylalkynylation of unactivated olefins. Based on the experimental results and literature reports, a possible reaction mechanism is proposed, which involvestert-butyl radical-triggered addition, 3-exo-dig cyclization of anti-“Baldwin” rule and alkynyl migration process. This reaction has the advantages of high functional group compatibility, metal-free conditions, and simple operation, which provides a feasible and effective synthetic strategy for the bifunctionalization of unactivated olefins.

Key words: alkynyl migration, 1,4-enynes, bifunctionalization, anti-baldwin rule