Development of Silylated Azadienes and Their Application to Heterocyclic Synthesis
| Project/Area Number |
60550593
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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 | Osaka University |
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Principal Investigator |
KOMATSU Mitsuo Osaka University Associate Professor, 工学部, 助手 (60029197)
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| Project Period (FY) |
1985 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1986: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1985: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | Silylated Azadienes / 1-Azadienes / Heterocyclic Synthesis / Functionalized Heterocycles / Azomethine Ylides / Cycloaddition / シクロ付加 |
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| Research Abstract |
Silylated azadienes were developed and applied to syntheses and functionalizations of heterocycles utilizing specific natures of the silyl group. Silylated imines were also studied as the closely related compounds.
1) A N-trimethylsilyl-1-azadiene was found to be an equivalent of a N-unsubstituted azadiene, which is hardly prepared. Thus a N-unsubstituted alkenyl- <beta> -lactam was prepared by the reaction of the azadiene and an ester enolate. The alkenyl <beta> -lactam was transformed to a thianonanam , a novel sulfur-containing bicylcic <beta> -lactam, by N-alkenylation followed by treatment with <SCl_2> .
2) Stereoselective thermal rearrangement of N-trimethylsilylimines to cis 2,3-disubstituted N-silylaziridines was found. The reaction intermediate is a N-silylazomethine ylide, which cycloadded to dipolarophiles to give pyrrolines.
3) N-Trimethylsilylmethyl-1-azadienes underwent rearrangement to N-silyl-2-pyrrolines which were isolated as 2-pyrrolines after hydrolysis. The N-silyl-azomethine ylide intermediates gave pyrrolines upon addition to dipolarophiles. The azadiene reacted with a ketene to give a functionalized <beta> -lactam.
4) A new method for generation of azomethine ylides from N-trimethylsilyl-methylamides methylamides was established via thermal rearrangement of the silyl group onto the oxygen atom. Various functinalized pyrroles and pyrrolines were prepared by cycloaddition of the ylides with dipolarophiles.
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Report
(1 results)
Research Products
(8 results)
