1997 Fiscal Year Final Research Report Summary
Synthesis of Optically Active Lysergic Acid
| Project/Area Number |
08672452
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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 | Toho University |
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Principal Investigator |
YOKOYAMA Yuusaku Toho University, Pharmaceutical Science, Associate Professor, 薬学部, 助教授 (10095325)
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| Project Period (FY) |
1996 – 1997
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| Keywords | biosynthesis / ergot alkaloids / tryptophan / Heck reaction / optically active / palladium catalyzed cyclization / DMAT / chanoclavine-I |
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| Research Abstract |
1.Total synthesis of optically acitive chanoclavine-I was successfully accomplished starting from optically active N_<alpha>-tert-butoxycarbony1-4-bromotryptophan methyl ester (1). The key step was the palladium catalyzed cyclization (Heck reaction) of alpha, beta-conjugate ester(2)which was obtained by the conversion of alpha-carboxyl group to aldehyde followed by Wittig reaction, to form tricyclic chclohexa [c, d] indole skeleton (ergoline skeleton).
2.Total synthesis of Y,Y-dimethylallyltryptophan (DMAT,3), which was the common intermediate of all ergot alkaloids biosynthesis, was accomplished starting from 1. The key step was Heck reaction of 1 with 1,1-dimethylallylalcohol (4) to form of N_<alpha>-tert-butoxycarbonyl-4- (2-hydroxy-2-methyl-1-butene-1-yl) -1-tosyltryptophan (5). Compound (5) was dehydrated with TsOH/benzene to form dine (6) which was converted to olefin (7) by 1,4-reduction with Mg/MeOH.
3.Decarboxylative cyclization 5 was failed under various conditions (radical or photo reactions of its thiol, selenol or oxime esters).
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[Publications] Y.Murakami, T.Watanade, H.Takahashi, H.Yokoo, Y.Kanazawa, M.Koshimizu, N.Adachi, M.Kurita, T.Yoshino, T.Inagaki, M.Ohishi, M.Watanade, M.Tani, Y.Yokoyama.: "Fischer Indolization of 2-Sulfonyloxypheny1-hydrazones : A New and Practical Approach for Preparing 7-Oxygenated Indoles and Application to the First Synthesis of Eudistomidin-A.(Fischer Indolization and its Related Compounds. Part)."
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