| Project/Area Number |
05640615
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Organic chemistry
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| Research Institution | SCIENCE UNIVERSITY OF TOKYO |
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Principal Investigator |
SATITO Takao SCIENCE UNIVERSITY OF TOKYO,CHEMISTRY,LECTURER, 理学部, 講師 (20084329)
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| Co-Investigator(Kenkyū-buntansha) |
MOTOKI Shinichi SCIENCE UNIVERSITY OF TOKYO,CHEMISTRY,PROFESSOR, 理学部, 教授 (00087339)
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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 |
¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1994: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1993: ¥800,000 (Direct Cost: ¥800,000)
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| Keywords | Thiocarbonyl Compound / Thiocarbonyl Ylide / Ortho-quinodimethane / Conjugated Carbodiimide / Thiaphosphole / Michael Addition Reaction / Diels-Alder Reaction / Electrocyclization / チアブタジエン / ジヒドロキナゾリン / 共役チオケトン / ヘテロディールス・アルダー反応 / 分子内ディールス・アルダー反応 |
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| Research Abstract |
1. The alpha, beta : gamma, delta-thiocarbonyl compounds derived from 2-(phenylthio)tetralinethione reacted thermally or in the presence of a Lewis acid catalyst with a variety of dienophiles to afford the polycyclic hetero Diels-Alder Cycloadducts in good yields. 2. Thiochalcone underwent asymmetric hetero Diels-Alder reactions with some chiral dienophiles to give the cycloadducts with high level of stereoselectivities in excellent yields. The absolute structure was determined. 3. The hetero Diels-Alder reaction of heteroaromatic thioketones with 2-chloroacrylonitrile or 2-haloacrylic esters afforded, after treatment of the cycloadducts with an amine, heterocycle-fused 2H-thiopyran compounds having an ortho-quinodimethane structure. 4. The intermediary thiocarbonyl ylides derived from the reaction of heteroaromatic thioketones with disulfonylcarbene species underwent 1,5-dipolar cyclization with elimination of a sulfinic acid to afford heterocycle-fused [c] thiophenes. 5.1,2-Thiaphospholes, prepared from the reaction of bicyclic trithiophosphates with tributylphosphine, underwent double Diels-Alder reactions with a variety of dienophiles or tandem Diels-Alder reaction/Michael addition reaction to give phosphorus-containing heterocycles. 6. The conjugated carbodiimides preferentially afforded the electrocyclization products under thermal conditions, whereas in the presence of a Lewis acid catalyst they gave the intramolecular Diels-Alder products in a highly periselective manner. 7. Addition reaction of the conjugated carbodiimides with a nucleophile such as an alcohol, an amine and a thiol, followed by intramolecular Michael addition reaction, gave the dihydroquinazoline derivatives.
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