1999 Fiscal Year Final Research Report Summary
Synthesis of Optically Active Allenecarboxylic Acid Derivatives by Asymmetric Carbonylation Reactions
| Project/Area Number |
09650958
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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 |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
IMADA Yasushi Graduate School of Engineering Science, Osaka University, Associate Professor, 大学院・基礎工学研究科, 助教授 (60183191)
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| Co-Investigator(Kenkyū-buntansha) |
今田 泰嗣 大阪大学, 大学院・基礎工学研究科, 助教授 (60183191)
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| Project Period (FY) |
1997 – 1999
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| Keywords | Carbon Monoxide / Carbonylation Reactions / Palladium Catalysts / Optically Active Phosphines / Kinetic Optical Resolutions / Allenylpalladium Complexes / Propargylic Esters / Oprically Active Allenes |
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| Research Abstract |
I have been studied carbonylation reactions of allylic and propargylic compounds. In this project, I studied asymmetric version of these carbonylation reactions to accomplish asymmetric carbon-carbon bond formation using carbon monoxide.
1. Carbonylation of allylic phosphates in the presence of a palladium complex catalyst bearing an optically active monodentate phosphine ligand proceeds smoothly to give optically active β, γ-unsaturated carboxlic acid esters. This is the first example of asymmetric version of allylic carbonylation reactions.
2. Optically active propargylic phosphates are carbonylated in the presence of a palladium complex catalyst with inversion of configuration to give axially chiral allenecarboxylic acid esters without loss of optical purity.
3. Carbonylation of racemic propargylic phosphates using a palladium complex catalyst bearing an optically active bidentate phosphine ligand proceeds with kinetic optical resolution to give axially chiral allenecarboxylic acid esters along with recovered optically active propargylic phosphates. This is the first example of asymmetric synthesis of allene compounds using a catalytic amount of chiral compound.
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