Studies on copper-catalyzed aerobic reactions of N-H imines
On investigating copper-catalyzed aerobic reactions of N-H imines, it was discovered that the iminyl copper species formed from reaction of Grignard reactions with carbonitriles, could undergo either C-H oxygenation or C-C bond cleavage depending on the starting material. The methylene C-H oxidation...
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| Format: | Theses and Dissertations |
| Language: | English |
| Published: |
2012
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| Online Access: | https://hdl.handle.net/10356/50839 |
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| Institution: | Nanyang Technological University |
| Language: | English |
| Summary: | On investigating copper-catalyzed aerobic reactions of N-H imines, it was discovered that the iminyl copper species formed from reaction of Grignard reactions with carbonitriles, could undergo either C-H oxygenation or C-C bond cleavage depending on the starting material. The methylene C-H oxidation provides 1,2-diacylbenzenes, which could be further transformed into phthalazines and isoindolines, while a C-C bond cleavage provides carbonitriles using pivalonitrile as a cyanide source. Both transformations are aided by the oxidation of the iminyl copper species with diradical oxygen to form a peroxycopper intermediate, followed by oxidation or homolytic cleavage to effect oxidation and C-C bond cleavage respectively. Both reactions could provide a range of desired products in respectable yields. |
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