Development of Asymmetric Reactions Catalyzed by Metal-Encapsulated Chiral Polysiloxane Gels
| Project/Area Number |
18550095
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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 |
Synthetic chemistry
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| Research Institution | Kyushu University |
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Principal Investigator |
MOTOYAMA Yukihiro Kyushu University, Institute for Materials Chemistry and engineering, Associate Professor (20283492)
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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 |
¥3,990,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥390,000)
Fiscal Year 2007: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2006: ¥2,300,000 (Direct Cost: ¥2,300,000)
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| Keywords | synthetic chemistry / catalysis-chemical process / supported catalyst / functional group-serective reaction / polymer gel / 触媒・化学プロセス / 分子認識 / 不斉反応 |
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| Research Abstract |
Immobilization of molecular catalysts on solid supports is an important approach in organic synthesis directed towards environmentally benign reaction processes. We have recently found that the metal-encapsulated polysiloxane gels ([M]@Si-O) are formed by Ru and Pt-catalyzed deoxygenative reduction of carboxamides with polymethylhydrosiloxanes (PMHSs) and catalyst species in the gels are still active towards deoxygenative reduction of carboxamides by addition of hydrosilanes. The purpose of this research is development of practical processes for stereo- and chemoselective organic transformations using catalyst-immobilized organogels. Ru and Pt-encapsulated polysiloxane gels (M@Si) were synthesized by treatment of PMHS with diols and dienes as a bridging reagent in the presence of transition metal complexes having dehydrogenative silylation or hydrosilylation activity. Triruthenium carbonyl cluster-encapsulated polysiloxane gels cross-linking with ethylene glycol or biphenol ([Ru_3]@Si-EG or ([Ru_3]@Si-BP) showed catalytic activity towards isomerization of alkenes. Double bond isomerization of allyl or homoallyl ethers using the present method followed by hydrolysis provided a practical method for deprotection of allyl and homoallyl ethers. Pt-encapsulated polysiloxane gel cross-linking with 1,5-hexadiene ([Pt]@Si-C_6) acted as efficient and reusable catalysts for nitro-selective reduction of functionalized nitroarenes. This procedure was applicable to production of anilines in gram-quantities. In these two cases, the product is separated from the gel catalyst by simple extraction, and catalyst species is not detectable in the product.
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Report
(3 results)
Research Products
(28 results)
