| Project/Area Number |
15205006
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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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 |
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Principal Investigator |
IWASAWA Nobuharu Tokyo Institute of Technology, Department of Chemistry, Professor, 大学院・理工学研究科, 教授 (40168563)
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| Project Period (FY) |
2003 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥40,690,000 (Direct Cost: ¥31,300,000、Indirect Cost: ¥9,390,000)
Fiscal Year 2005: ¥12,350,000 (Direct Cost: ¥9,500,000、Indirect Cost: ¥2,850,000)
Fiscal Year 2004: ¥12,090,000 (Direct Cost: ¥9,300,000、Indirect Cost: ¥2,790,000)
Fiscal Year 2003: ¥16,250,000 (Direct Cost: ¥12,500,000、Indirect Cost: ¥3,750,000)
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| Keywords | Metal-Containing Carbonyl Ylide / Matal-Containing Azomethine Ylide / Tungsten Carbonyl / [3+2] Cycloaddition Reaction / Carbene Complex / Electrophilic Activation of Alkynes / Geminal Carbo-functionalization / Rhenium Carbonyl / 三環性インドール / [5+2]付加環化反応 / ビシクロ[3.3.0]オクタン / ビシクロ[5.3.0]デカン / 塩化白金 / 臭化金 / ジエノールシリルエーテル / タングステンカルボニル錯体 / レニウムカルボニル錯体 / タングステン含有カルボニルイリド / 多機能性反応活性種 / タングステン含有アゾメチンイリド / 多環性インドール誘導体 / 1,2,5-ヘキサジエン / Cope型転位反応 / o-エチニル安息香酸エステル / 白金含有カルボニルイリド |
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| Research Abstract |
In this research, generation and reaction of novel multi-functional reactive species are studied extensively. It is expected that electiophilic activation of alkynes with W(CO)_5(L) followed by attack of nucleophiles on them would give novel multi-functional reactive species, which are expected to behave both as a 1,3-dipole and as a carbene complex. Based on this concept, several unique and synthetically useful reactions have been developed.
In the first place, generation and reaction of novel tungsten-containing carbonyl and azomethine ylides were developed. Treatment of ο-ethynylphenyl ketones or N-(ο-alkynylphenyl)imine derivatives with W(CO)_5(thf) generated the tungsten-containing 1,3-dipoles by the endo-mode of attack of the carbonyl oxygen or imino nitrogen onto the electrophilically activated alkyne moiety. The [3+2]-cycloaddition of the generated ylides with electron-rich alkenes followed by insertion of the resulting tungsten carbene moiety into a neighboring C-H bond or 1,2-
… More
alkyl-migration realized the construction of complex cyclic carbon frameworks in a single step. This reaction proceeded even with a catalytic amount of W(CO)_5(thf). Thus, novel multi-functional reactive species are successfully generated and react with alkenes to give synthetically useful compounds in a single operation.
We next examined the possibility of realizing geminal carbo-functionalization of alkynes. Treatment of ω-acetylenic dienol silyl ethers with W(CO)_6 under photoirradiation gave bicyclo[3.3.0]octane derivatives, which were produced by addition of the silyl enol ether to the electrophilically activated alkynes to give alkenylmetallic intermediates. This further reacted with α,β-unsaturated oxonium moiety at the position β to the metal to give carbene complex intermediates, which underwent typical carbene reactions to give the products. This method constitutes a catalytic method for the geminal carbo-functionalization of alkynes. ReCl(CO)_5 showed paiticularly high activity for this reaction ; even 0.5〜3.0 mol% of ReCl(CO)_5 were sufficient to promote the reaction efficiently. Less
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