| Project/Area Number |
11672135
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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 | The Institute of Physical and Chemical Research |
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Principal Investigator |
NAKATA Tadashi The Institute of Physical and Chemical Research, Synthetic Organic Chemistry Lab., Chief Scientist, 有機合成化学研究室, 主任研究員 (50087524)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUO Goh The Institute of Physical and Chemical Research, 有機合成化学研究員, 研究員 (10300899)
MATSUKURA Hiroko The Institute of Physical and Chemical Research, 有機合成化学研究員, 先任技師(研究職)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2000: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1999: ¥2,500,000 (Direct Cost: ¥2,500,000)
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| Keywords | Brevetoxin / Polycyclic ether / Samarium diiodide / Tetrahydropyran / Oxepane / Convergent synthesis / Two-directional synthesis / Iterative synthesis / 4環性エーテル / ブレベトキシンB / 海洋産多環状エーテル / 環化反応 / トランス縮環 / アルコキシアクリレート |
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| Research Abstract |
Since the first isolation of brevetoxin B, a neurotoxin produced by the red tide organism Gymnodinium breve, many marine polycyclic ethers of this type have been reported. The most characteristic structural feature of these natural products is trans-fused polycyclic ether ring system. The synthetically challenging unique structures and their potent biological activities have attracted the attention of numerous synthetic organic chemists.
In this project, we have developed an extremely facile and highly efficient strategy for the iterative synthesis of a trans-fused polytetrahydropyran ring system based on the SmI_2-induced reductive intramolecular cyclization. This method is also effective for the synthesis of polycyclic ether ring systems including oxepane and also an angular methyl group. Based on the present SmI_2-induced cyclization, a strategy for two directional synthesis of polycyclic ether was developed.
A very efficient convergent strategy for the construction of the trans-fused 6-6-6-6-membered tetracyclic ether ring system was developed based on the acetylide-triflate coupling of two tetrahydropyrans, oxidation of the alkyne group to an a-diketone, double cyclization to 6,6,6,6-membered tetracyclic diacetal, and stereoselective reduction of the diacetal with Et_3SiH-TMSOTf.
In conclusion, we have developed very simple and efficient strategies for the construction of trans-fused polycyclic cyclic ether ring system. This strategy would be widely applicable to efficient syntheses of natural polycyclic ethers
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