| Project/Area Number |
17590008
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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 | KYUSHU UNIVERCITY |
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Principal Investigator |
SUEMUNE Hiroshi Kyushu University, Faculty of Pharmaceutical Sciences, Professor, 大学院薬学研究院, 教授 (20095897)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2005: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Keywords | Intermolecular Reaction / Hydroacylation / Catalytic Reaction / Rhodium Complex / Ketone Synthesis / キレーション |
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| Research Abstract |
We reported in 2004 that an intermolecular hydroacylation between salicylaldehydes and 1,4-penta-or 1,5-hexa-dienes by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso-and normal-hydroacylated products. The above findings prompted us to study this reaction to develop a practical synthetic reaction in connection with stereoselectivity and regioselectivity.
1. Rh-catalyzed π-facial selective intermolecular hydroacylation of norbornenes
Rh-catalyzed π-facial selective intermolecular hydroacylation of norbornenes with salicylaldehydes have been attained. In the reaction with norbornylene, the exo-hydroacylated product was produced selectively because of steric hindrance. In the case of norbornadiene, the endo-product was obtained stereoselectively because of chelation effect. Additionally, because of chelation effect and remote substituent effects, the product formed in the reaction of 7-tert-butoxynorbornadiene was the endo, syn-product. Thus, the stereoselective hydroacylation could be achieved.
2. Nitrile-promoted Rh-catalyzed intermolecular hydroacylation of olefins with salicylaldehyde
Rh-catalyzed intermolecular hydroacylation of salicylaldehyde and alkenylnitriles has been found to proceed at room temperature and to preferentially give normal-hydroacylated products. Addition of acetonitrile and sodium acetate accelerated the Rh-catalyzed hydroacylationof monoolefines to exclusively produce the normal-hydroacylated products under miled reaction conditions. Plausible reaction mechanisms for the regioselections are also proposed. Thus, the generality of this reaction could be widely developed.
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