| Project/Area Number |
11555240
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 展開研究 |
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| Research Field |
有機工業化学
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| Research Institution | Nagasaki University |
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Principal Investigator |
TAMARU Yoshinao Nagasaki University, Professor, 工学部, 教授 (80026319)
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| Co-Investigator(Kenkyū-buntansha) |
BANDO Takashi Sumitomo Pharmaceutical Co. Researcher, 研究員
OKAJIMA Toshiya Saga University, Associate Professor, 文化教育学部, 助教授 (60224002)
KIMURA Masanari Nagasaki University, Assistant Professor, 工学部, 助手 (10274622)
福田 勉 長崎大学, 工学部, 助手 (80295097)
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| Project Period (FY) |
1999 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥13,800,000 (Direct Cost: ¥13,800,000)
Fiscal Year 2002: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2001: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2000: ¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 1999: ¥4,200,000 (Direct Cost: ¥4,200,000)
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| Keywords | allenes / [2+2] cycloaddition / exazolidinone / alkenes / alkynes / alcohols / Woodward-Hoffmann rule / indoles / sulfonamide / Diels-Alder / オキサゾリジノン / 複素環化合物 / スピロ化合物 / 環化付加 / 転位反応 / 環化付加反応 |
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| Research Abstract |
The allene bond of allene carbamate (1, 4-vinylidene-2-oxazolidinone) shows a chameleonic reactivity, changing the reaction patters widely depending on the kinds of its reaction partners. With terminal alkenes and alkynes, 1 undergoes [2+2]cycloaddition in a concerted manner and provides methylene cyclobutanes and methylenecyclobutenes. Respectively in good yields. The cycloaddition proceeds under strictly thermal activation conditions (70-100 ℃) with retention of the configuration of the alkene double bonds. Usually, [2+2]cycloaddition is a thermally forbidden process and the unique reactivity of 1 is explained on the basis of a [2π+2π+2π] Huckel transition state. With enols and allylsilanes, 1 undergoes unique 1,3-sulfonyl migration followed by the inverse electron demand Diels-Alder reaction giving rise to tetrehydropyridine derivatives. With silanes (RnSiH4-n, n = 1-3), alcohols, and thiols, 1 undergoes the 1,3-sulfonyl migration and provides a variety of 4-propylidene-2- oxazolidinones in excellent yields.
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