2007 Fiscal Year Final Research Report Summary
Development of Indium-and Platinum-catalyzed Reactions for Environmentally Benign Organic Synthesis
| Project/Area Number |
17550094
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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 | University of Tsukuba |
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Principal Investigator |
MIURA Katsukiyo University of Tsukuba, Graduate School of Pure and Applied Sciences, Associate Professor (20251035)
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| Co-Investigator(Kenkyū-buntansha) |
HOSOMI Akira University of Tsukuba, Professor Emeritus (00004440)
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| Project Period (FY) |
2005 – 2007
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| Keywords | Platinum / Indium / Environmentally Benign Synthesis / Silicon Reagent / Allylation / Cyclic Ether / Radical Reaction / Conjugated Enone |
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| Research Abstract |
We have developed new reactions using platinum and indium catalysts for environmentally benign organic synthesis as shown below.
1. Allylation of Carbon Electrophiles with Vinylsilanes: It was found that vinylsilanes were smoothly isomerized to allylsilanes under catalysis by platinum salts. This isomerization was successfully utilized for allylation of carbon electrophiles with vinylsilanes, which is more convenient than the known method using allylsilanes because of easy access to vinylsilanes.
2. Annulation between Alkenols and Aldehydes: In the presence of catalytic amounts of PtCl_2 and AgOTf, 5-methyl-5-hexen-1-ols reacted efficiently with aldehydes to give tetrahydropyrans (THPs). This annulation is useful for atom-economical, stereoselective synthesis of multi-substituted THPs.
3. Allylation of Acetals with Alkenes: The PtCl_2-AgX catalyst system enabled an ene-type allylation of acetals with 1, 1-disubstituted alkenes. This allylation provides a convenient, direct route to homoallyl ethers.
4. Radical Reactions of Haloalkanes with Hydrosilanes: It was found that a catalytic amount of In (Oac)_3 effectively promoted radical reduction of haloalkanes with PhSiH_3 under very mild reaction conditions. The In (Oac)_3-PhSiH_3 system was successfully utilized for radical addition of haloalkanes to alkenes. The present method is environmentally more benign than the known method using toxic organotin hydrides.
5. Carbonyl Metathesis-type Reaction of Alkynes with Aldehydes: The In (Otf)_3-catalyzed reaction of arylalkynes with aromatic aldehydes gave chalcones in good yield. The carbonyl metathesis-type reaction could be applied to an efficient cyclization of alkynals.
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[Journal Article] Silicon Lewis Acids2008
Author(s)
三浦勝清
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Journal Title
New Acid Catalysis in Modern Organic Synthesis ed. By H. Yamamoto and K. Ishihara", Vol.1, " Chap.9", Elsevier," Amsterdam
Pages: 469-516
Description
「研究成果報告書概要(和文)」より
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[Journal Article] Silicon Lewis Acids2008
Author(s)
K. Miura and A. Hosomi
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Journal Title
New Acid Catalysis in Modern Organic Synthesis ed. by H. Yamamoto and K. Ishihara, Wiley-VCH, Weinheim, Germany Vol.1, Chap.9
Pages: 469-516
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Silicon2007
Author(s)
三浦勝清
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Journal Title
Comprehensive Organometallic Chemistry III ed. by R. H. Crabtree and M.p. Mingos", Vol.9, " Chap.7.", Elsevier," Amsterdam
Pages: 297-339
Description
「研究成果報告書概要(和文)」より
-
[Journal Article] Silicon2007
Author(s)
K. Miura and A. Hosomi
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Journal Title
Comprehensive Organometallic Chemistry III ed. by R. H. Crabtree and M. P. Mingos, Elsevier, Amsterdam Vol.9, Chap.7
Pages: 297-339
Description
「研究成果報告書概要(欧文)」より
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