2006 Fiscal Year Final Research Report Summary
Generation of Selective Organometallic Reagents
| Project/Area Number |
17550035
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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 |
Organic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
SHIBATA Ikuya Osaka University, Center for Environmental Preservation, Professor, 環境安全研究管理センター, 教授 (10196420)
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| Project Period (FY) |
2005 – 2006
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| Keywords | Indium / Reduction / Control of Selectivity / Metal Exchange / Active Species |
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| Research Abstract |
Dihalogenoindium hydrides (X_2InH) are novel reducing reagents, which act in both an ionic and a radical manner. The hydrides were easily generated from InX_3 and Bu_3SnH to reduce a variety of functionalities such as aldehydes, ketones, enones, and imines. One-pot treatment of Cl_2InH, enones, and aldehydes achieved reductive aldol reactions, in which the predominant reduction of enones was followed by an aldol reaction between the resulting indium enolates and the remaining aldehydes. It is noteworthy that both anti-and syn-selective aldols were obtained by the use of THF and an aqueous solvent, respectively. The replacement of Bu_3SnH into Et_3SiH as a hydride source allowed the catalytic use of InBr_3 to give the syn-selective aldols. The dehalogenation of alkyl halides was achieved by a catalytic amount of InCl_3 in the presence of Bu_3SnH. This procedure was applied to some representative cyclizations as radical proof A simple and non-toxic system, NaBH_4/InCl_3,also promoted dehalogenation, intramolecular cyclization, and intermolecular coupling reactions. In addition, the Et_3SiH/InCl_3 system was found applicable to an effective intramolecular cyclization of enynes.
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Research Products
(19 results)
