2016 Fiscal Year Final Research Report
Catalytic Chemoselective introduction of Unprotected-Amino group for the Synthesis of alpha-Amino Acids
| Project/Area Number |
15K14930
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Chemical pharmacy
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| Research Institution | Kyushu University |
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Principal Investigator |
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| Project Period (FY) |
2015-04-01 – 2017-03-31
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| Keywords | 有機化学 / 非天然アミノ酸 / 化学選択性 / アミノ化 / ナイトレノイド / 銅触媒 |
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| Outline of Final Research Achievements |
In order to synthesize α-amino acid derivatives directly from carboxylic acid equivalents, we developed a first general catalytic α-amination of carboxylic acid oxidation state pronucleophile.
We focused on the bidentate coordinative acylpyrazole and iminoiodinane for the simultaneous activation of both the nucleophile and the electrophile. The bidentate coordination mode enabled chemoselective enolization over readily enolizable ketones and much more acidic nitroalkyl functionality. This is the first catalytic chemoselective deprotonative activation method of a carboxylic acid oxidation state pronucleophile over a highly acidic nitroalkyl functionality. In addition, the present catalysis could be applicable to late-stage α-amination of complex molecules. Mechanistic studies revealed that highly reactive copper nitrenoid species with a radical character was crucial for obtaining the product in high yield.
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| Free Research Field |
有機化学
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