Development of Amphiphilic Resin-Supported Catalysts Realizing Water-Based Organic Synthesis
| Project/Area Number |
11470472
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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 |
Chemical pharmacy
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| Research Institution | Institute for Molecular Science (2000)
Nagoya City University (1999) |
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Principal Investigator |
UOZUMI Yasuhiro Institute for Molecular Science, Professor, 分子科学研究所, 教授 (90201954)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 2000: ¥4,200,000 (Direct Cost: ¥4,200,000)
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| Keywords | ansition metal catalysts / palladium-phosphine complexes / amphiphilic solid support / organic transformation in water / PS-PEG resin / palladium catalysis / PS-PEG レジン |
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| Research Abstract |
New amphiphilic resin-supported triarylphosphines (PEP) were designed and prepared on polyethylene glycol-polystyrene graft copolymer (PEG-PS). The PEG-PS resin-supported palladium-monophosphine complex Pd(PEP) was readily prepared by treatment of PEP with an excess amount of di(m-chloro)bis(h3-allyl) dipalladium(II) ([PdCl(h3-C3H5)]2) (Pd/P > 1/1) followed by removal of unimmobilized [PdCl(h3-C3H5)]2 by washing. Palladium complexe Pd(PEP) catalyzed allylic substitution of 3-acetoxy-1,3-diphenyl-1-propene and cinnamyl acetate with various nucleophiles including 1,3-dicarbonyl compounds, amino acids, sodiumazide, and sodium sulfinate, to give quantitative yields of corres ponding allylic substituted products in water.
The hydroxycarbonylation reaction of aryl or alkenyl halides also took place in aqueous alkaline solution under an atmospheric pressure of carbon monoxide at 25 。C in the presence of 3 mol % palladium of an amphiphilic resin-supported palladium-phosphine complexe bound to a
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polyethylene glycol-polystyrene graft copolymer (PEG-PS resin) (Pd(PEP). The reaction of aryl halides gave correspond-ing benzoic acids in quantitative yields. Pd-PEP also catalyzedHeck reaction of iodobenzene with acrylic acid to give cinnamic acid in 92%yield. No organic solvent was used for the reactions and no chromatographical purification was re-quired to obtain the products. The resin-supported catalyst was recovered by filtration and reused. No loss of catalytic activity was observed during 30 runs. The cross-coupling reaction of aryl halides or allyl acetates with arylboronic acids or sodium tetraphenylborate was catalyzed in water by the Pd(PEP) catalyst. The reaction of aryl halides with arylboron reagents in the presence of 2 mol% palladium of Pd(PEP) in aqueous alkaline solution at 25 。C gave corresponding biphenyl derivatives in high yields. Pd(PEP) also catalyzed allylic arylation of allyl acetates (including 1,3-disubstituted allyl acetates and cyclic allyl acetates) with arylboron reagents in water under the similar reaction conditions to give 80-99% yield of allylarenes. Less
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Report
(3 results)
Research Products
(25 results)
