| Project/Area Number |
07405042
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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 |
Synthetic chemistry
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| Research Institution | KYOTO UNIVERSITY (1997-1998)
Tokyo Institute of Technology (1995-1996) |
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Principal Investigator |
HIYAMA Tamejiro Kyoto University Graduate School of Engineering Professor, 工学研究科, 教授 (90026295)
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| Co-Investigator(Kenkyū-buntansha) |
SHIMIZU Masaki Kyoto University Graduate School of Engineering Instructor, 工学研究科, 助手 (10272709)
白川 英二 京都大学, 工学研究科, 助手 (70273472)
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| Project Period (FY) |
1995 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥33,300,000 (Direct Cost: ¥33,300,000)
Fiscal Year 1998: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1997: ¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 1996: ¥8,800,000 (Direct Cost: ¥8,800,000)
Fiscal Year 1995: ¥16,600,000 (Direct Cost: ¥16,600,000)
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| Keywords | Oxidative Desulfurization-Fluorination / Organofluorine Compounds / Organosiliocn Compounds / Cross Coupling Reaction / Transmetalation / Carbostannylation / Trifluoromethylation / palladium Catalyst / シラノール / パラジウム / 銅 / ジフルオロオレフィン / フルオロプーメラ転位 / 有素ケイ素化合物 / 塩化アリール / 有機フッ素化合物 / 酸化的脱硫フッ素化 / キサントゲン酸エステル / トリフルオロメチルエーテル / ビニルエポキシド / 水酸化ナトリウム / 環状アリルシラン / フッ化物イオン / フルオロプ-メラ-転位 / 不斉クロスカップリング反応 / 光学活性アリルシラン / 不斉転写 / トリフルオロメチルアミン型液晶化合物 |
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| Research Abstract |
(1) Oxidative Desulfurization Fluorination
Upon reaction with an oxidant like a positive halogen, organosulfur compounds gives sulfonium ions whose C-S bonds are weaked to undergo nucleophilic substitution readily. A fluoride ion of 70% HF/Py and Bu_4NH_2F_3 replaces sulfur to give organofluorine compounds. In this way, trifluoromethyl-substituted aromatics and olefins, trifluoromethyl ethers, trifluoromethylamines, alpha-fluoro sulfides, and vis-difluoro olefins are shown to be readily available from the corresponding organosulfur precursors.
(2) Cross-Coupling Reactions with Organosilicon Compounds
This novel reaction is now called as the Hiyama Coupling. Although a trimethylsilyl group is pertinent to vinylsilanes, SiFMe_2 or SiF_2 Me is necessary for alkenylsilanes in general.
Alkoxysilanes also are applicable. As a coupling partner, aryl chlorides are now shown to be applicable.
Transmetalation from silicon to copper(I) is now achieved in DMF.Thus, alkynylsilanes couple with halobenzenes or dimerizes oxidatively using a palladium catalyst. Conjugate reduction of alpha, beta-unsaturated esters and ketones is attained with hydrosilanes.
(3) Cross-Coupling and Carbostannylation with Organotin Compounds
Using a novel catalyst consisting of palladium and an imino phosphine ligand, organotin compounds are shown to readily undergo cross-coupling reactions, oxidative dimerization, and carbostannylation to acetylenes.
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