Generation of [1,n]-dipolar intermediates and their reactions
| 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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Report
(4 results)
Research Products
(52 results)
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[Presentation] Fitst Total Synthesis of Prunustatin A2015
Author(s)
Shuhei Yamkoshi, Masako Okamoto, Eiji Kawanishi, Michiko Sasaki, Kei Takeda
Organizer
The 13th International Kyoto Conference on New Aspects of Organic Chemistry
Place of Presentation
Kyoto
Year and Date
2015-11-09
Related Report
Int'l Joint Research
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