| Project/Area Number |
61850153
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
KIITIRO UTIMOTO Kyoto University, Faculty of Engineering, Professor, 工学部, 教授 (90025958)
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| Co-Investigator(Kenkyū-buntansha) |
KAZUHIKO TAKAI Kyoto University, Faculty of Engineering, Instructor, 工学部, 助手 (00144329)
KOICHIRO OSHIMA Kyoto University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (00111922)
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| Project Period (FY) |
1986 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥11,600,000 (Direct Cost: ¥11,600,000)
Fiscal Year 1987: ¥4,900,000 (Direct Cost: ¥4,900,000)
Fiscal Year 1986: ¥6,700,000 (Direct Cost: ¥6,700,000)
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| Keywords | Heterocycles / Transition Metal Catalyst / Indole / Piperidine / Prostaglendin / Hydrostannylation / Perfluotoalkylalkenes / フッ素化合物 / バラジウム / 遷移金属触媒 / 付加環化 / ピロリジン / アセチリド / 二酸化炭素 / アルカロイド |
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| Research Abstract |
Novel syntheses of heterocycles by transition metal-catalyzed intramolecular addition cyclization have been extensively studied.
(1) Novel synthesis of indoles: 3-allylindoles are synthesized by palladium catalyzed allylative cyclization of 2-alkynylanilines with allyl chloride. Analogously, 3-bromoindoles are obtained by Pd-catalyzed reaction of 2-alkynylanilines with Nbromousuccinimide.
(2) Tetrahydropyridines from alkynylamines: Palladium (II) or golf (III) catalyzed cyclization of 5-alkynylamines produces 2,3,4,5-tetrahydropyridines in excellent yields. This reaction will open novel access to optically active alkaloids starting from optically active alkynylamines.
(3) Caboxylative allylation: Carboxylative cyclization of lithium salt of propargylic alcohols and successive allylation with allyl chlorides proceed smoothly under palladium catalysis. As lithuim salt or propagylic alcohols cam be prepared by the reaction of lithium acetylide with cardonyl compounds, this procedure opens novel route to the introduction of acyl anion equivalent to carbonyl compounds.
(4) Palladium catalyzed regioselective hydration of acetylenes: Under intramolecular assistance of carbonyl group, acetylenes can be hydrated regioselectively under mild conditions. This procedure can be applied to acid sensitive substrates such as prostaglandims.
(5) Palladum catralyzed hydrostannylation: Acetylened and allenes can by hydeostannylated under mild conditions by palladium catalysis.
(6) Synthesis of Organofluoro Compounds: Palladuim catalzed coupling of vinltin compounds with perfluoroalkyl iodide bives fluorinated olefins.
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