1988 Fiscal Year Final Research Report Summary
Synthesis of Optically and Biologically Active Compounds Using Tartaric Acid as Chiral Source.
| Project/Area Number |
62570945
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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 |
Chemical pharmacy
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| Research Institution | Gifu Pharmaceutical University |
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Principal Investigator |
YUKIO Masaki Gifu Pharmaceutical University, 薬学部, 教授 (20082977)
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| Co-Investigator(Kenkyū-buntansha) |
HIROHISA Oda Gifu Pharmaceutical University, 薬学部, 助手 (30106439)
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| Project Period (FY) |
1987 – 1988
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| Keywords | tartaric acid / 6,8-dioxabicyclo[3.2.1]octane / house mouse pheromone / 2-sec-buty1-thiazoline / alpha-conhydrine / p-anisyloxymethyl group / asymmetric synthesis / 化学選択的脱臭素オレフィン化反応 |
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| Research Abstract |
1. Optically active bicyclic compounds (3<@D5-@>D5) were synthesized in 47-55% overall yield from 4-tosyl-2-butanone or 3-tosylpropanal and diethyl ester (2<@D5-@>D5) of tartaric acid (1<@D5-@>D5) in four steps. Site selective bromination of 3<@D5-@>D5 followed by chemoselective debromo-olefination reaction with zinc gave olefins (4<@D5-@>D5). Both enantiomers of 4<@D5-@>D5 were utilized for synthesis of the house mouse pheromone (4<@D5-@>D5'). 2. Oxidation of olefins (4<@D5-@>D5 R<@D11@>D1=H, R<@D12@>D1=OMs, OBn) with MCPBA afforded stereoselectively the alpha-epoxides (5<@D5-@>D5). Isomerization of 5<@D5-@>D5 to allylic alcohol derivatives followed by the Claisen rearrangement gave the amides (6<@D5-@>D5), which appear to be promising intermediates for synthesis of pharmacologically active prostanoids. 3. In order to investigate pheromonal activities of optically active 4<@D5-@>D5', boomers of 2-sec-butylthiazoline (7<@D5-@>D5) which has been known to be one of the major synergists of the pheromone were synthesized in 60% ee from (S)-(-)-2-methyl-1-butanol and (R)-(-)-methyl 2-hydroxymethylpropanoate, respectively. 4. Synthesis of alpha-conhydrine (10<@D5-@>D5), one of the hemlock alkaloid compoments, has been studied. Partial ring opening of the antipode of 3<@D5-@>D5 (R<@D5-@>D1=H, R<@D12@>D1=OMs) afforded the pyranoid (8<@D5-@>D5), which was converted into the azide-ester (9<@D5-@>D5). The alkaloid (10<@D5-@>D5) will soon be synthesized from 9<@D5-@>D5. 5. In our synthetic works on biologically active natural products, p-anisyloxymethl (p-AOM) group was developed as a novel oxidatively removable acetal type OH-protecting group.
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