Synthetic Studies on Physiologically Active Marine Terpenoids
| Project/Area Number |
60470031
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
天然物有機化学
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| Research Institution | Faculty of Science, Osaka City University |
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Principal Investigator |
TOKOROYAMA Takashi Faculty of Science, Osaka City University, 理学部, 教授 (90046938)
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| Co-Investigator(Kenkyū-buntansha) |
IIO Hideo Faculty of Science, Osaka City University, 理学部, 助手 (80145771)
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| Project Period (FY) |
1985 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1987: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1986: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1985: ¥5,800,000 (Direct Cost: ¥5,800,000)
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| Keywords | Agelasines / synthesis / Folding strain control / Terpenic chain / Hypotaurocyamine derivative / cis-Clerodane diterpene / Furanocembranolide / Dihydropukalide / 立体特異的合成 / 生理活性海産ジテルペノイド / 分子内Diels-Alder反応 / lophotoxin / pukalide / furanocembranolide / 不斉合成 |
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| Research Abstract |
This studies concerns with syntheses of two types of marine diterpenoids, which are attractive from the views of their unique structures adn interesting physiological activities.
Synthesis of agelasines: Agelasine F and agelasidine C are respectively 9-methyl- 7-adenylium and hypotaurocyamine derivatives of common terpenic moiety. For the stereoselective synthesis of the ring part we studied the cyclization reaction of 8-trimethylsilyl-6-octanal extending our methodology on the remote control in ringclosure reactions (folding strain control). The ring part thus obtained was coupled with extra C_9-terpenic chain by a palladium-mediated reaction to afford the diterpene moiety. The terpenic unit as bromide was connected with the adenine ring regioselectively by the previously developed method and the total synthesis of agelasine F has completed. For the synthesis of agelasidine C, we investigated first the method to introduce the hypotaurocyamine group to terpenic unit using farnesyl bromide as model. Then application of the procedure thus established we succeeded in the synthesis of agelasidine C from the diterpenic synthon above. In connection with the synthesis of agelasine A, the one-pot stereospecific procedure for the construction of cis-clerodane skeletone was developed and successfully applied to the total synthesis of linaridial.
Synthesis of lophotoxins: The macro-cyclizaion method for the construction of furanocembranolide was explored. The formation reaction of a trisubstituted furan ring was used for the ring-closure and thus the furanocembrane skeletone could be constructed in a simple way in a mederate yield. Next the synthesis of dihydropukalide was pursued. L-carvone and D-glutamic acid was utilized as chiral sources. Feasibility of this approach has been demonstrated by the synthesis of a furanocembranolide derivative, which could be a useful intermediate.
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Report
(2 results)
Research Products
(12 results)
