Syntheses of Heterocycles Utilizing Trimethylsilyldiazomethane
| Project/Area Number |
07672281
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | Nagoya City University |
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Principal Investigator |
AOYAMA Toyohiko Nagoya City University, Faculty of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (80080191)
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| Project Period (FY) |
1995 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1995: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Keywords | trimethylsilyldiazomethane / lithium trimethylsilyldiazomethane / alkylidene carbene / 2-oxo-3-pyrroline / 3-pyrroline / 2-pyrroline / pyrrole / benzofuran / o-シロキフェニルアセチレン / C-H挿入反応 |
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| Research Abstract |
Synthesis of heterocycles utilizing trimethylsilyldiazomethane (TMSCHN_2) , a useful reagent for generating alkylidene carbenes from carbonyl compounds, was investigated as follows :
1. Lithium trimethylsilyldiazomethane (TMSC(Li)N_2), easily prepared from TMSCHN_2 with n-BuLi or LDA,smoothly reacted with N,N-dialkylamides of alpha-keto acids and N,N-disubstituted alpha-amino ketones to give 2-oxo-3-pyrrolines (C-H insertion products) and 3-pyrrolines (C-H insertion products) in good yields via alkylidene carbene intermediates, respectively.
2. TMSC (Li) N_2 easily reacted with beta-amino ketones to give 2-pyrrolines (N-H insertion products) in good yields, which easily underwent oxidation by treatment with manganese dioxide (CMD,chemical manganese dioxide) to afford the corresponding pyrroles.
3. TMSC (Li) N_2 smoothly reacted with o-siloxybenzaldehydes and o-siloxyacetophenones to give the corresponding o-siloxyphenylacetylenes via alkylidene carbene intermediates, which afforded benzofurans in good yields by treatment with tetrabutylammonium fluoride. Furthermore, 3-benzofuranmethanols could be obtained when the reaction was performed in the presence of electrophiles such as aromatic and heteroaromatic aldehydes.
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Report
(3 results)
Research Products
(10 results)
