| Project/Area Number |
10440185
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Tokyo Institute of Technology (1999)
The University of Tokyo (1998) |
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Principal Investigator |
IWASAWA Nobuharu Graduate School of Science and Engineering, Tokyo Institute of Technology, Professor, 大学院・理工学研究科, 教授 (40168563)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 1999: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥3,000,000 (Direct Cost: ¥3,000,000)
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| Keywords | endo cyclization / tungsten carbonyl / vinylidene / electrocyclization / propargylmalonate / silyl enol ether / タングステンカルボニル錯体 / エキソ環化 / エンド環化 / ビシクロ[n.3.0]骨格 / ビシクロ[n.4.0]骨格 / タングステンペンタカルボニル / エンド選択的環化反応 / ビニリデン錯体 |
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| Research Abstract |
A novel W(CO)ィイD25ィエD2-catalyzed endo selective cyclization of ω-acetylenic silyl enol ethers was developed. It was expected that treatment of ω-acetylenic silyl enol ethers with W(CO)ィイD25ィエD2・THF would generate electrophilic alkyne-W(CO)ィイD25ィエD2 complexes and/or their isomerized vinylidene complexes and that intramolecular attack of the silyl enol ether part on the tungsten-coordinated alkyne would occur to give cyclized product. In practice, the reaction proceeded as expected and endo cyclized product was obtained selectively in most cases with a catalytic amount of the complex. Furthermore, even in the case of the reaction where exo cyclization was favored under the similar reaction conditions, endo product was obtained as a major product by choosing appropriate reaction conditions. This reaction was further expanded to the annulation of five- or six-membered ring onto α,β-unsaturatred ketones by the combination of 1,4-addition of propargylmalonate with trapping the produced enolates as silyl enol ethers, followed by the W(CO)ィイD25ィエD2-catalyzed cyclization.
By treatment of benzenes ortho-substituted with an alkenyl group and a terminal acetylene with 5 mol% amount of W(CO)ィイD25ィエD2・THF, 6π-electrocyclization proceeded via tungsten vinylidene intermediates to give naphthalene derivatives in high yields. This reaction was further applied to the facile synthesis of various hetero-polyaromatics.
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