1993 Fiscal Year Final Research Report Summary
Development of New Methods for Carbonylation by Free-Radical Reactions
| Project/Area Number |
04453087
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Osaka University |
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Principal Investigator |
SONODA Noboru Osaka Univ., Faculty of Engineering, Professor, 工学部, 教授 (20083983)
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| Co-Investigator(Kenkyū-buntansha) |
AKIYA Ogawa Osaka Univ., Faculty of Engineering, Research Assistant, 工学部, 助手 (30183031)
RYU Ilhyong Osaka Univ., Faculty of Engineering, Research Assistant, 工学部, 助手 (80210821)
KAMBE Nobuaki Osaka Univ., Faculty of Engineering, Associate Professor, 工学部, 助教授 (60144432)
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| Project Period (FY) |
1992 – 1993
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| Keywords | free-radical / carbonylation / carbon monoxide / tin radical / silyl radical / formylation / cyclization / acyl radical |
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| Research Abstract |
A novel carbonylation method based on free-radical reactions has been developed. Acylradicals, generated by the addition of alkyl free-radicals to carbon monoxide, have been effectively trapped by tin hydride. Through this sequence, the free-radical formylation of organo halides to the corresponding aldehydes was realized. When an alkene was also present in the reaction system, the trapping of the alkyl free-radical by carbon monoxide to form an acyl free-radical and the subsequent addition of that radical to the alkene took place efficiently to give and unsymmetrical ketone. Tris(trimethylsily)silane can also be used for a free-radical mediator. This sequence represents a unique method for the double alkylation of carbon monoxide. Carbonylative cyclizations to give cyclopentanones can also be affected starting with 4-pentenyl halides. All of these findings that free-radical carbonylation is useful method for the introduction of carbon monoxide into organic molecules.
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