| Project/Area Number |
05554022
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
物質変換
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| Research Institution | University of Tsukuba |
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Principal Investigator |
HOSOMI Akira University of Tsukuba, Chemistry, Professor, 化学系, 教授 (00004440)
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| Co-Investigator(Kenkyū-buntansha) |
ARATANI Tadatoshi Sumitomo Chemical Industries, Co.Led., Research Manager, 有機合成研究所, 主席研究員
TOMINAGA Yoshinori Nagasaki University, Chemistry, Assistant, 薬学部, 助手 (70100881)
MIURA Katsukiyo University of Tsukuba, Chemistry, Assistant, 化学系, 助手 (20251035)
HOJO Makoto University of Tsukuba, Chemistry, Lecturer, 化学系, 講師 (50229150)
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| Project Period (FY) |
1993 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥5,500,000 (Direct Cost: ¥5,500,000)
Fiscal Year 1994: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1993: ¥4,500,000 (Direct Cost: ¥4,500,000)
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| Keywords | Di-exo-methylene compound / Fused isoxazoles / [4+2] Cycloaddition / [2+2] Cycloaddition / 1,2,3-Butatriene / 1,3-Elimination / 1,3-Dipolar reagent / [3+2] Cycloaddition / 立体特異的合成 / テトラヒドロフラン / 有機ケイ素化合物 / 高選択的有機合成 / ジ-エキソ-メチレン化合物 / 1,4-脱離反応 / (トリメチルシリルメチル)アセチレンカルボン酸メチル / ニトリルオキシド / 〔3+2〕環化付加 / イソオキサゾール誘導体 |
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| Research Abstract |
1.Synthesis of new di-exo-methylene compounds and fused isoxazoles
We have prepared and used methyl (trimethylsilylmethyl) acetylenecarboxylate as a dipolarophile and a common key compound leading to precursors for di-exo-methylene compounds which subsequently react with olefins in [4+2] cycloaddition mode to afford fused heterocyclic compounds. We found a new and general route toward the synthesis of the precursor for di-exo-methyleneisoxazolines and their Diels-Alder reactions leading to fused isoxazoles.
2.New access to di-exo-methylenecyclobutanes via [2+2] cycloaddition of 3-methylthio-4-trimethylsilyl-1,2-butadiene with alkenes mediated by a Lewis acid
In the course of studies in organic synthesis using allylsilanes and propargylsilanes, we found a new and general route toward the synthesis of di-exo methylenecyclobutanes via the [2+2] cycloaddition of 3-methylthio-4-trimethylsilyl-1,2-butadiene with alkenes promoted by a Lewis acid followed by sequential reactions to sulfones by oxidation and 1,2-elimination. Di-exo-methylenecyclobutanes were also successfully applied to construct a bicyclo [5.2.0] nonane ring system by the [4+3] cycloaddition with an 2-oxyallyl cation. The title compound can be viewed formally as a synthetic equivalent of 1,2,3-butatriene or 1,3-butadien-2,3-diyl.
3.Creation and Reactions of Carbonyl Ylides and Related 1,3-Dipolar Reagents
1,3-Dipolar reagents are important and interesting chemical species from both synthetic and theoretical points of view. We found that the novel findings that simple carbonyl ylides, otherwise inaccessible, were indeed expediently generated by the silicon-based 1,3-elimination from alpha-aryl-substituted chloromethyl trimethylsilylmethyl ether under mild and neutral conditions which provided the powerful one-step synthesis of dihydrofurans and tetrahydrofurans and related heterocylesvia[3+2]cycloadditions to a vareity of multiple pi-bonds including C=C,C*C,C=O,C=S,C=N,N=N.
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