Copper-Catalyzed Amination of Indoles via C-H Bond Activation

• Main Authors: Ming-kai Pan, 潘明楷
• Other Authors: Ming-Jung Wu
• Format: Others
• Language: zh-TW
• Published: 2012
• Online Access: http://ndltd.ncl.edu.tw/handle/39667571567544279708

碩士 === 國立中山大學 === 化學系研究所 === 100 === A new protocol for direct amination of N-Methyl-2-phenylindole catalyzed by copper(II) trifluoromethanesulfonate was presented. Both of (E)-N-(1,1''-Dimethyl-2,2'' -diphenyl-2,3''-biindolin-3-ylidene)-4-methylbenzenesulfonamide（4）and 4-methyl -N-(1-methyl-2-phenyl-1H-indol-3-yl)benzenesulfonamide（2）were obtained under the optimal reaction conditions (2.5 mol% Cu(OTf)2, 1.2 equiv PhI=O, 0.7 equiv PhI=NTs heated at 25 ℃ in acetonitrile for 1 hour) in 78 % and 11 % yields, respectively. In addition, (E)-N-(2-hydroxy-1-methyl-2-phenylindolin-3-ylidene)-4-methylbenzene sulfonamide （6）and (E)-N-(1,1''-dimethyl-2,2''-diphenyl-2,3''-biindolin-3-ylidene) -4-methylbenzenesulfonamide （4）were synthesized in 47 % and 24 % yields, respectively, by using 5 mol% Cu(OTf)2, 2 equiv PhI=O, 1.2 equiv PhI=NTs at ambient temperature in acetonitrile for 1 hour. Finally, 4-methyl-N-(1-methyl-2-oxo-3-phenyl indolin-3-yl)benzenesulfonamide （3）and 1,1''-dimethyl-2,2''-diphenyl-2,3''-biindolin -3-one （7）can be formed under the following reaction condition, 5 mol% Cu(OTf)2, 2 equiv PhI=O, 1.2 equiv PhI=NTs and 3 equiv Ag2CO3 heated at 100 ℃ in acetonitrile for 1 hour, in 41% and 22% yields, respectively.