2005 Fiscal Year Final Research Report Summary
Asymmetric Construction of Bicyclic [3.1.0] Compounds and Its Application
| Project/Area Number |
15590007
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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 | Okayama University |
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Principal Investigator |
ABE Hitoshi Okayama University, Advanced Science Research Center, Associate Professor, 自然生命科学研究支援センター, 助教授 (70221728)
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| Project Period (FY) |
2003 – 2005
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| Keywords | Baker's yeast / Asymmetric synthesis / Kinetic optical resolution / Deprotonation reaction / Amide base |
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| Research Abstract |
Highly stereoselective syntheses of chiral bicyclic [3.1.0] compounds have been developed by several methods. On a way of this research project, some total syntheses of natural products were also achieved by a palladium-mediated biaryl coupling reaction of phenyl benzoate derivatives.
1.A Reaction of σ-Symmetric Ketone Compounds
A symmetric ketone was prepared as the substrate, through the Meinwald rearrangement of norbornadiene. An enentioselective deprotonation reaction was attempted using several chiral amide bases. This reaction was quite successful to produce an optically active bicycle[3.1.0] compound with high enantioselectivity.
Next, a symmetric epoxyketone was examined on the enantioselective deprotonation reaction using chiral amide bases. This reaction was also successful to generate the corresponding enolate followed by a transannular carbon-carbon bond formation accompanying an epoxy opening. The obtained product was transformed into the optically active bicyclo[3.1.0] compound with high optical purity.
2.Optical Kinetic Resolution Using the Baker's Yeast
An optical kinetic resolution of a racemic bicyclo[3.1.0] compound using the baker's yeast was attempted. After various examination of the reaction conditions and work-up methods, we found that this technique was effective to give the optical active bicycle[3.1.0] compound with high stereoselectivity. The optical purity and the absolute configuration were determined by comparison with a reported information.
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