| Project/Area Number |
25460015
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | Hiroshima University |
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Principal Investigator |
Sasaki Michiko 広島大学, 医歯薬保健学研究院(薬), 准教授 (30379888)
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| Project Period (FY) |
2013-04-01 – 2016-03-31
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| Project Status |
Completed (Fiscal Year 2015)
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| Budget Amount *help |
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2013: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
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| Keywords | 有機合成 / 合成化学 / 三員環 / 1,n-双極子 / 環化反応 / 三員環化合物 / 開環反応 / 1,4-双極子 |
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| Outline of Final Research Achievements |
With the aim of developing a method that allows the generation of [1,n]-dipolar intermediates, we focused on base-induced ring-opening reactions of 2-(p-tosylmethyl)cyclopanecarboxylate. When the cyclopropane derivative was treated with LiN(SiMe3)2 in the presence of alkylidenemalonate, a cyclopentenecarboxylate derivative, which lacks a tosyl and a methoxycarbonyl groups, was obtained in high yields. We propose a mechanism for a newly developed reaction that involves (1) a Michael addition of a 1,3-dipolar intermediate generated by a base-induced ring opening to the malonate, (2) the formation of a five-membered ring bearing a p-tosylmethylcarbanion moiety via an intramolecular Michael reaction of the generated malonate anion to an α,β-unsaturated sulfone moiety, (3) the formation a four-membered ring by intramolecular attack of the carbanion to an ester carbonyl group, and (4) the formation of cyclopentenecarboxylate by liberation of p-tosylacetate via a formal cycloreversion.
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