Development of Novel Reformatsky Reaction by Using Lewis Acid-Reductant.
| Project/Area Number |
13650900
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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 |
有機工業化学
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| Research Institution | The University of Tokyo |
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Principal Investigator |
HASHIMOTO Yukihiko The University of Tokyo, School of Engineering, Associate Professor, 大学院・工学系研究科, 助教授 (50201710)
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| Project Period (FY) |
2001 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2004: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2003: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2001: ¥1,000,000 (Direct Cost: ¥1,000,000)
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| Keywords | Lewis acid / Phosphine / the Reformatsky Reaction / the Claisen Condensation / the Mannich Reaction / α-Bromacarbonyl compounds / Sulfoxide / α-Diketone / 四塩化チタン / 脱酸素化 / 不斉配位子 / 速度論的光学分割 / イミン / α-ヒドロキシケトン / チオエステル / アセタール / 立体選択的反応 / α-ブロモケトン / α-ブロモチオエステル / トリo-トリルホスフィン |
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| Research Abstract |
We have found that the reduction of α-bromoamide could be achieved under mild conditions using Lewis acid and phosphine combination. Also, it has been already reported that the Reformatsky-type reaction could proceed when the aldehyde was reacted with the intermediate metal enolate, to give the desired β-hydroxyamide in good yield with high stereoselectivity. In this research, we would like to develop the synthetically useful reactions using this methodology.
At first, the Reformatsky reaction using α-bromoketones or thioesters, instead of α-bromoadmides, were investigated. As a result, the desired Reformatsky-type products were obtained in good yield with high stereoselectivity by using the combination of titanium tetrachloride and tri-o-tolylphosphine. Next, this reaction was applied to the other electrophile such as thioesters, acetals, and imines. The reaction with thioester have smoothly proceeded to give the reductive-Claisen condensate, and the Mannich-type reaction with imine was also found to give the corresponding adducts in good yield with high stereoselectivity. Moreover, other reductive reactions were also examined and we found the half-reduction of α-diketones, deoxygenation of sulfoxides and so on. Especially, the later was applied to the kinetic resolution of racemic phosphines to give optically active phosphines.
We found the several useful carbon-carbon bond forming reactions, reductive functional group interconversions using this combined reagent system. It was found that the combined reagent system was useful in the field of organic synthesis.
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Report
(5 results)
Research Products
(12 results)
