有机化学 ›› 2018, Vol. 38 ›› Issue (1): 190-199.DOI: 10.6023/cjoc201708046 上一篇    下一篇

所属专题: 庆祝吴养洁院士九十华诞专辑

研究论文

金催化的扩环反应:2,3-苯并二氮杂(艹卓)类化合物的高效合成

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 E-mail:sunning@sioc.ac.cn;yhliu@sioc.ac.cn
  • 基金资助:

    国家自然科学基金(Nos.21572256,21372244,21421091)、国家重点研发计划(No.2016YFA0202900)及中国科学院战略性先导科技专项(B类)(No.XDB20000000)资助项目.

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 E-mail:sunning@sioc.ac.cn;yhliu@sioc.ac.cn
  • 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).

研究了金催化的基于1-炔基-1,2-二氢-2,3-二氮杂萘类底物的氧化/扩环反应,在以PPh3AuNTf2为催化剂8-甲基喹啉氮氧化物为氧化剂的条件下高效地合成了2,3-苯并二氮杂(艹卓)类化合物.该反应可能经历了α-羰基金卡宾的生成以及选择性的1,2-苯基迁移反应,而1,2-H和1,2-N迁移反应未观测到.我们还研究了2,3-苯并二氮杂(艹卓)类产物在FeCl3存在下的转化反应,发现随着FeCl3的用量的不同,可以分别生成吡唑及多并环类产物.

关键词: 金催化, 氧化, 扩环反应, 2,3-苯并二氮杂(艹卓)

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