Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (1): 190-199.DOI: 10.6023/cjoc201708046 Previous Articles     Next Articles

Special Issue: 庆祝吴养洁院士九十华诞专辑



胡辉, 胡晓苹, 陈铭, 孙宁, 刘元红   

  1. 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 中国科学院大学 上海 200032
  • 收稿日期:2017-08-23 修回日期:2017-09-25 发布日期:2017-10-11
  • 通讯作者: 孙宁, 刘元红;
  • 基金资助:


Gold-Catalyzed Ring Expansion Reaction: Highly Efficient Synthesis of Functionalized 2, 3-Benzodiazepine Scaffolds

Hu Hui, Hu Xiaoping, Chen Ming, Sun Ning, Liu Yuanhong   

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Inistitute of Organic Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, Shanghai 200032
  • Received:2017-08-23 Revised:2017-09-25 Published:2017-10-11
  • Contact: 10.6023/cjoc201708046;
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21572256, 21372244, 21421091), the National Key R&D Program of China (No. 2016YFA0202900) and the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000).

A gold-catalyzed oxidative ring expansion of 1-alkynyl-1,2-dihydrophthalazines has been developed. The reaction was catalyzed by PPh3AuNTf2in the presence of 8-methylquinoline N-oxide as the oxidant, leading to 2,3-benzodiazepine derivatives with high efficiency. The reaction likely proceeds through the formation of α-carbonyl gold carbene and 1,2-migration of a phenyl group, while no 1,2-H and 1,2-N migration take place. Further transformation of 2,3-benzodiazepine products in the presence of FeCl3 was also carried out, pyrazole and polyfused heterocycle were formed, respectively, through variation of the amounts of FeCl3.

Key words: gold catalysis, oxidation, ring expansion, 2,3-benzodiazepine