1997 Fiscal Year Final Research Report Summary
New chiral sources for asymmetric synthesis
| Project/Area Number |
08672428
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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 | KYUSHU UNIVERSITY |
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Principal Investigator |
SUEMUNE Hiroshi KYUSHU UNIVERSITY,FACULTY OF PHARMACEUTICAL SCIENCES,PROFESSOR, 薬学部, 教授 (20095897)
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| Project Period (FY) |
1996 – 1997
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| Keywords | asymmetric synthesis / enzymatic hydrolysis / asymmetric reaction / diol / optically active compound |
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| Research Abstract |
Following results were obtained through this project.
1) Asymmetric induction into meso-1,3-diacetoxy-5-cycloheptene by PFL-catalyzed hydrolysis afforded monoacetate (1S,3R)-6 of 97% enantiomeric excess (e.e.), which was converted into a synthetic equivalent of delta-lactone moiety in mevinic acid derivatives.
2) Asymmetric transesteriflcation of meso-spirodiol using Pseudomonas fluorescens lipase gave the corresponding monoacetate of high enantiomeric excess, from which the formal synthesis of (-) -curcumanolide A was achieved.
3) Total synthesis of furoscrobiculin B,a lactarane sesquiterpene isolated from basidiomycetes of mushurooms, was achieved via an improved synthetic route of our previous work based on a Furan Ring Transfer reaction and base-catalyzed pinacol-type rearrangement.
4) Pseudomonas fluorescens lipase-catalyzd asymmetric hydrolysis of meso-2,5-bis (acetoxymethyl) -3,4- (isopropylidenedioxy) tetrahydrofuran afforded the optically active correponding monoacetate of 92% e.e. in 94% yield. The absolute configuration was determined to be 2S,3S,4R,5R by chemical correlation with D-allose.
5) Optically active 5-cyclooctene-1,2-diol derivatives prepared by enzymatic procedure have been converted into bicyclo [3.3.0] octane derivatives by transannular reaction with complete inversion of stereogenic center attached by a leaving group. Formal synthesis of (+) -iridomyrmecin has been achieved starting from (S,S) -5-cyclooctene-1,2-diol by using this process.
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