Rh(III)催化的N-甲氧基苯甲酰胺系列物选择性C-H氰基化反应

doi:10.1016/S1872-2067(15)60872-5

催化学报 ›› 2015, Vol. 36 ›› Issue (8): 1175-1182.DOI: 10.1016/S1872-2067(15)60872-5

Rh(III)催化的N-甲氧基苯甲酰胺系列物选择性C-H氰基化反应

张斯维^a,b, 周杰^b, 施晶晶^b, 王旻^a, 徐华强^b,c, 易伟^b

a 中国药科大学生命科学与技术学院, 江苏南京210009;
b 中国科学院上海药物研究所, 中科院受体结构与功能重点实验室药物靶标与结构功能研究中心, 上海201203;
c Van Andel研究所结构科学与药物发现中心, 美国密西根49503

收稿日期:2015-04-14 修回日期:2015-04-21 出版日期:2015-07-29 发布日期:2015-07-30
通讯作者: 徐华强, 易伟
基金资助:
上海市自然科学基金(15ZR1447800); 国家博士后科学基金(2012M511158, 2013T60477, 2014M560363).

Rh(III)-catalyzed direct C-H cyanation of N-methoxybenzamides using N-cyano-N-phenyl-p-toluenesulfonamide

Siwei Zhang^a,b, Jie Zhou^b, Jingjing Shi^b, Min Wang^a, H. Eric Xu^b,c, Wei Yi^b

a School of Life Science and Biotechnology, China Pharmaceutical University, Nanjing 210009, Jiangsu, China;
b VARI/SIMM Center, Center for Structure and Function of Drug Targets, CAS-Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203, China;
c Laboratory of Structural Sciences, Program on Structural Biology and Drug Discovery, Van Andel Research Institute, Grand Rapids, Michigan 49503, USA

Received:2015-04-14 Revised:2015-04-21 Online:2015-07-29 Published:2015-07-30
Supported by:
This work was supported by Shanghai Municipal Natural Science Foundation, China (15ZR1447800) and the Chinese Postdoctoral Science Foundation (2012M511158, 2013T60477, 2014M560363).

摘要/Abstract

摘要：

采用了最近热门的Rh(III)催化C-H键活化方法, 以N-甲氧基苯甲酰胺系列物为反应底物, N-氰基-N-苯基对甲苯磺酰胺(NCTS)为氰基化试剂, 高效合成了含氰基官能团产物. 结果表明, 该反应在碳酸银存在下, 使用二氧六环作为反应溶剂, 于80 ℃反应8 h生成的邻位氰基取代的N-甲氧基苯甲酰胺的产率较高. 进一步研究表明, 该反应具有好的区域选择性和底物/官能团适应性. 一系列机理实验研究表明, 该反应可能采用了一个内部的亲电取代机制及使用了C-H键切割步骤作为关键限速步骤. 考虑到该反应产物包含有价值的结构单元-N-甲氧基甲酰胺和氰基取代基, 因而有望用于现代有机合成中.

关键词: Rh(III)催化剂, C-H键氰基化, N-甲氧基苯甲酰胺系列物, N-氰基-N-苯基对甲苯磺酰胺, 反应机制

Abstract:

A new method has been developed for the mild and efficient Rh(III)-catalyzed direct C-H cyanation of a diverse range of N-methoxybenzamides using N-cyano-N-phenyl-p-toluenesulfonamide as an environmentally friendly and efficient cyanating reagent. This new reaction proceeded with good regioselectivity to provide direct access to a wide variety of valuable ortho-cyanated N- methoxybenzamides with board substrate/functional group tolerance.

Key words: Rhoduim(III) catalyst, C-H cyanation, N-methoxybenzamides, N-cyano-N-phenyl-p-toluenesulfonamide, Reaction mechanism

张斯维, 周杰, 施晶晶, 王旻, 徐华强, 易伟. Rh(III)催化的N-甲氧基苯甲酰胺系列物选择性C-H氰基化反应[J]. 催化学报, 2015, 36(8): 1175-1182.

Siwei Zhang, Jie Zhou, Jingjing Shi, Min Wang, H. Eric Xu, Wei Yi. Rh(III)-catalyzed direct C-H cyanation of N-methoxybenzamides using N-cyano-N-phenyl-p-toluenesulfonamide[J]. Chinese Journal of Catalysis, 2015, 36(8): 1175-1182.

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Rh(III)催化的N-甲氧基苯甲酰胺系列物选择性C-H氰基化反应

Rh(III)-catalyzed direct C-H cyanation of N-methoxybenzamides using N-cyano-N-phenyl-p-toluenesulfonamide

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