Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (10): 4050-4058.DOI: 10.6023/cjoc202105044 Previous Articles     Next Articles

ARTICLES

铱催化异羟肟酸衍生物参与的分子间N—N键偶联反应合成酰肼

宋方方, 朱士阳, 王浩*(), 陈弓*()   

  1. 南开大学 元素有机化学国家重点实验室 天津 300071
  • 收稿日期:2021-05-25 修回日期:2021-06-22 发布日期:2021-07-05
  • 通讯作者: 王浩, 陈弓
  • 基金资助:
    国家自然科学基金(21725204); 国家自然科学基金(21901127); 中国博士后科学基金(2018M640225); 中国博士后科学基金(2019T120179)

Iridium-Catalyzed Intermolecular N—N Coupling for Hydrazide Synthesis Using N-Benzoyloxycarbamates as Acyl Nitrene Precursor

Fangfang Song, Shiyang Zhu, Hao Wang(), Gong Chen()   

  1. State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071
  • Received:2021-05-25 Revised:2021-06-22 Published:2021-07-05
  • Contact: Hao Wang, Gong Chen
  • Supported by:
    National Natural Science Foundation of China(21725204); National Natural Science Foundation of China(21901127); China Postdoctoral Science Foundation(2018M640225); China Postdoctoral Science Foundation(2019T120179)

An iridium-catalyzed intermolecular N—N coupling reaction using various N-benzoyloxyamides as acyl nitrene precursor for hydrazide synthesis has been developed. Unlike the carboxylic acid-derived dioxazolones used in previous report, this type of precursors allows the efficient synthesis of both acyl and oxycarbonyl substituted hydrazines from readily accessible precursors. Computational chemistry studies indicated that formation of the metal-acylnitrenoid intermediates via intramolecular hydrogen bond-assisted N—O cleavage may be the rate-determining step, and the subsequent nucleophilic attack of metal-acylnitrenoid by arylamines may be assisted by Cl…HN hydrogen bond to form the N—N bond.

Key words: iridium catalysis, nitrene, N—N coupling, hydrazide, N—H insertion