Development of Highly Stereoselective Asymmetric Reactions Using P-Chiral Phosphine Ligands
| Project/Area Number |
18350017
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Chiba University |
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Principal Investigator |
IMAMOTO Tsuneo Chiba University, Graduate School of Science, Chemistry, Professor (10134347)
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| Co-Investigator(Kenkyū-buntansha) |
YOSHIDA Kazuhiro Chiba University, Graduate School of Science, Chemistry, Assistant Professor (60375607)
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| Project Period (FY) |
2006 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥16,480,000 (Direct Cost: ¥14,800,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2007: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2006: ¥9,200,000 (Direct Cost: ¥9,200,000)
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| Keywords | P-Chiral Phosphine / Optically Active Phosphine Ligand / Catalytic Asymmetric Synthesis / Asymmetric Hydrogenation / Optically Active Compound / Phosphine-borane / Chiral Rodium Complex / Chiral Palladium Complex / P-キラルポスフィン / 光学活性ボスフィン配位子 / ホスフィンボラン / 遷移金属錯体 / エナンチオ選択性 / 光学活性パラジウム錯体 |
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| Research Abstract |
This study is directed toward the development of new asymmetric catalysts that exhibit exceedingly high enantioselectivity and catalytic activity. In order to achieve this purpose, we designed and prepared new P-chiral phosphine ligands based on the phosphine-borane methodology. The newly synthesized phosphine ligands (QuinoxP^* and AlkynylP^*) have been proved very high enantioselectivities up to 99.9% ee in not only rhodium-catalyzed asymmetric hydrogenation but also rhodium- or palladium-catalyzed carbon-carbon bond forming reactions.
A new synthetic method for the synthesis of the counter enantiomers of P-chiral phosphine ligands has been studied. A key intermediate (S)-t-butylmethylphosphine-borane, which is prepared by the use of (-)-sparteine, was converted to (R)-enantiomer by the bromination and reduction with lithium aluminum hydride. The synthesized (R)-enantiomer was used for the preparation of (R,R) t-Bu- QuinoxP^*.
Mechanistic study was carried out in order to investigate the enantioselection mechanism in the rhodium-catalyzed asymmetric hydrogenation of dehydroaminoacids using (Z)-α-acetamidocinnamate as a model substrate and R-(tert-butylmethylphosphino)(di-tert-butylphosphino)methane as the chiral ligand. Based on the experimental facts and DFT caluculation, it is concluded that the enantioselection takes place during the association step when the chelating dihydride is formed from the nonchelating dihydride.
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Report
(3 results)
Research Products
(16 results)
