| Project/Area Number |
04640534
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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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 | Okayama University of Science |
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Principal Investigator |
UENISHI Junichi Okayama University of Science Faculty of Science, Associate professor, 理学部, 助教授 (50167285)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1993: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1992: ¥1,600,000 (Direct Cost: ¥1,600,000)
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| Keywords | iododiene / organometallic reagent / polyene / terpenoid / dehydrodendrolasin / ircinianin / stereospecific reaction / インエン / 付加反応 |
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| Research Abstract |
Addition of MeMgSnBu^n3 reagent to a terminal enyne proceeded at-20ﾟC stereospecifically. The produced bimetallodiene was successively trapped by an electrophile such as alky halides, oxiranes and cyclic enones to give the corresponding 2-substituted 1-tributylstannyldiene. Due to an instability of the stannyldienes against moistures of acids, it was immediately quenched with iodine to afford 1-iodo-2-alkyl-1,3-diene. This manipulation allows a facile preparation of 2-substituted 1-iodo-2-alkyl-1,3-dienes derived from enynes substrates. The iododienes are synthetically useful, particularly for preparations of substituted polyene derivatives. Potential synthetic applications for two marine natural furano-terpenoids, dehydrodendrolasin and irucinianin were accomplished in this reseach.
1)Synthesis of Dehydrodendrolasin Dehydrodendrolasin is unstable furano-terpenoid isolated from Pleraphysilla spinifera. This natural product was synthesized from 3-furaldehyde in 10 steps, including the above key reaction step of 5-(3-furano)-3-penten-1-yne.
2)Synthesis of Ircinianin Ircinianin was the first polycyclic sesterterpenetetronic acid isolated from a marine sponge of the genus Ircinia. The structure was revealed by X-ray diffraction method of the single crystals. A synthesis of ircinianin methyl ether was performed in 11 steps from 5-(3-furano) pentyne. The important iodotriene intemediate was obtained from dienyne using the above stereospeciffic reaction.
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