1990 Fiscal Year Final Research Report Summary
Preparation of Optically Active Allylic Amine Derivatives
| Project/Area Number |
01550648
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Kyoto University |
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Principal Investigator |
TOSHIMITSU Akio Kyoto University, Institute for Chemical Research, Instructor, 化学研究所, 助手 (60127107)
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| Co-Investigator(Kenkyū-buntansha) |
UEMURA Sakae Kyoto University, Institute for Chemical Research Associate Professor, 化学研究所, 助教授 (70027069)
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| Project Period (FY) |
1989 – 1990
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| Keywords | Amidoselenation / Enantioselectivity / Allylic Amine |
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| Research Abstract |
For the study of the substitution reaction of hydrogen atom on the carbon atom bearing the arylseleno group by the carbon nucleophile, the nature of the protecting group on the nitrogen atom was found to be important. As the amides containing acyl group were susceptible to side reactions, we decided to to use p-toluenesulfonyl group as the protecting group. The preparatin of the starting materials required a bit of study and we discovered for the first time the amidoselenation reaction using p-toluenesulfonamide as the nitrogen nucleophile. The characteristic feature of this reaction is the use of the Lewis acid as the catalyst and we found that zinc (II) chloride is suitable for this reaction. Beta-Amide-Selenides thus prepared were oxidized at low temperature to selenoxide and deprotonated by the reaction with lithium diisopropylamide. Subsequent alkylation was found to proceed by the reaction with alkyl or allyl halides at low temperature. Low-temp-pair-stirrer which was purchased by this Grant was used effectively at this stage of our research. By rasing the reaction temperature to ambient, the selenoxide elimination reaction proceeded to afford allylic amides selectively. It was confirmed that the products were not contaminated by its regioisomer, vinylic amides.
The application of this procedure to the asymmetric amides would complete our purpose of this research project. Due to the shor of time we could not yet complete this program, but our results of these two years would allow any researcher to carry out this work.
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