| Project/Area Number |
09650958
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | Osaka University |
|---|
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)
|
|---|
| 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)
|
|---|
| Project Period (FY) |
1997 – 1999
|
| Project Status |
Completed (Fiscal Year 1999)
|
| Budget Amount *help |
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 1999: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥2,300,000 (Direct Cost: ¥2,300,000)
|
|---|
| Keywords | Carbon Monoxide / Carbonylation Reactions / Palladium Catalysts / Optically Active Phosphines / Kinetic Optical Resolutions / Allenylpalladium Complexes / Propargylic Esters / Oprically Active Allenes / 速度論的光学分割 / 光学活性アレン化合物 / π-アリルパラジウム錯体 / 一酸化酸素 / π-アリルパラジウム / アレニルパラジウム / アレン化合物 |
|---|
| 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.
|
