有机化学 ›› 2018, Vol. 38 ›› Issue (7): 1687-1694.DOI: 10.6023/cjoc201802004 上一篇    下一篇

研究论文

铑催化酸酐对氧杂苯并降冰片烯的不对称开环反应研究

胡继荣a, 徐建斌a, 邹玲玲a, 吕海平a, 樊瑞峰b, 刘娜a, 周永云a, 樊保敏a,b   

  1. a 云南民族大学 云南民族大学-香港浸会大学传统天然药物研发联合实验室 昆明 650500;
    b 云南民族大学 民族药资源化学国家民委-教育部重点实验室 昆明 650500
  • 收稿日期:2018-02-02 修回日期:2018-03-27 发布日期:2018-04-12
  • 通讯作者: 徐建斌, 樊保敏 E-mail:xujianbin@ruc.edu.cn;adams.bmf@hotmail.com
  • 基金资助:

    国家自然科学基金(No.21572198)和云南省应用基础研究计划重点(No.2017FA004)资助项目.

Rhodium Catalyzed Asymmetric Ring-Opening Reaction of Oxabenzonorbornadienes with Anhydride

Hu Jironga, Xu Jianbina, Zou Linglinga, Lü Haipinga, Fan Ruifengb, Liu Naa, Zhou Yongyuna, Fan Baomina,b   

  1. a Yunnan Minzu University-Hong Kong Baptist University Joint Laboratory of Traditional Natural Medicine, Yunnan Minzu University, Kunming 650500;
    b Key Laboratory of Chemistry in Ethnic Medicinal Resources, Yunnan Minzu University, Kunming 650500
  • Received:2018-02-02 Revised:2018-03-27 Published:2018-04-12
  • Contact: 10.6023/cjoc201802004 E-mail:xujianbin@ruc.edu.cn;adams.bmf@hotmail.com
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21572198) and the Applied Basic Research Project of Yunnan Province (No. 2017FA004).

过渡金属催化的氧杂苯并降冰片烯的不对称开环反应是合成含有四氢化萘骨架结构的有效方法之一,许多传统的亲核试剂被用于该反应中,并取得了一系列优异的结果.酸酐作为常用的酰基化试剂,其对氧杂苯并降冰片烯的不对称开环反应可以合成许多重要的手性化合物,而该反应目前尚无报道.通过研究发现,离子型Rh(COD)2BF4与手性二茂铁类配体(R,S)-PPF-PtBu2的配合物可以高效地催化酸酐对氧杂苯并降冰片烯的不对称开环反应.在经过一系列的条件优化后,该铑催化体系表现出优秀的催化活性,能够催化含有多种取代基的氧杂苯并降冰片烯与乙酸酐和丙酸酐的不对称开环反应,并取得了最高94%的收率和对映体过量值为95%ee的结果.

关键词: 铑, 催化, 氧杂苯并降冰片烯, 酸酐, 不对称开环反应

Transition metal catalyzed asymmetric ring-opening reaction (ARO) of oxabenzonorbornadienes is a useful tool in the formation of carbon-carbon bond or carbon-heteroatom bond, which have attracted extensive study and received great achievements over the past decades. A series of efficient catalysts have been established and the high-level control of enantioselectivity for these reactions have been realized. A wide range of nucleophiles including carbon and heteroatom nucleophiles have been used in this reaction. Anhydride is a common acylation reagent and there has been no report about the ARO reaction of oxabenzonorbornadienes with anhydride, which can generate some useful chiral compounds. In this work, Rh-catalyzed ARO of oxabenzonorbornadienes with acetic anhydride and propionic anhydride have been developed. The developed protocol could result in ARO product in high yield (up to 94%) and excellent enantioselectivity (up to 95% ee).

Key words: rhodium, catalysis, oxabenzonorbornadiene, anhydride, asymmetric ring-opening reaction