| Project/Area Number |
12672056
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | Gifu Pharmaceutical University |
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Principal Investigator |
KATAOKA Tadashi Gifu Pharmaceutical University, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (00082975)
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| Co-Investigator(Kenkyū-buntansha) |
WATANABE Shinichi Gifu Pharmaceutical University, Faculty of Pharmaceutical Sciences, Research Assistant, 薬学部, 助手 (40275095)
IWAMURA Tatsunori Gifu Pharmaceutical University, Faculty of Pharmaceutical Sciences, Lecturer, 薬学部, 講師 (70184900)
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| Project Period (FY) |
2000 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2001: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2000: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Keywords | Baylis-Hillman reaction / sulfide / Lewis acid / Michael reaction / aldol reaction / halomethylene aldol / alkyne / β-haloacrylic acid ester |
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| Research Abstract |
In order to overcome the drawback of the Baylis-Hillman reaction, "the slow rate," we developed the chalcogemde-TiCl_4-mediated tandem Michael-aldol reactions. The reactions had been deemed to be a chalcogene version of the Baylis-Hillman reaction, because the Baylis-Hillman adducts were given after purification of the products by the preparative TLC on silica gel. However, the initial products were α-chloromethyl aldols and were dehydrochlorinated during purification by the preparative TLC. The reactions of S-ethyl thioacrylate and keto esters gave much better results than the Baylis-Hillman reactions of ten. The reactions of acetylenic ketones and esters produced α-chloromethylene aldols. The chalcogenides were necessary for the reactions of α,β-unsaturated esters. The reactions of acetylenic ketones and esters and α-keto esters did not occur when tertiary amines were used as a catalyst instead of a Chalcogenide and TiCl_4.
We next studied the reaction in which a chalcogenide worked as Lewis base and found that sulfanyl substituent intramolecularly added to an enone to form a cychc sulfomum betaine. The tandem Michael-aldol reactions of 1- [2-(methylsulfanyDphenyl]prop-2-en-1-one or the seleno congener with aldehydes in the presence of BF_3・E_2O gave the Baylis-Hillman adduct and onium salt, and 3-(α-hydroxybenzyl) selenochromanone from the seleno congener.
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