| Project/Area Number |
06453137
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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 |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
RYU Ilhyong Osaka Univ., Faculty of Engineering, Associate Professor, 工学部, 助教授 (80210821)
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| Co-Investigator(Kenkyū-buntansha) |
SONODA Noboru Osaka Univ., Faculty of Engineering, Professor, 工学部, 教授 (20083983)
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| Project Period (FY) |
1994 – 1995
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| Project Status |
Completed (Fiscal Year 1995)
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| Budget Amount *help |
¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1995: ¥900,000 (Direct Cost: ¥900,000)
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| Keywords | delta-lactone / carbon monoxide / saturated alcohol / radical carbonylation / lead tetraacetate / remote functionalization / 1,5 hydrogen shift / alkoxy radical |
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| Research Abstract |
In this work, a novel straightforward method for the synthesis of delta-lactones has been pursued. Taking advantage of the lead tetraacetate-induced oxidation of alcohols, a novel delta-lactone synthesis from saturated alcohols and CO was achieved. This remote carbonylation is quite general for primary and secondary alcohols whose delta-carbons are primary or secondary. In case of an alcohol having both primary and secondary delta-carbons, carbon monoxide is incorporated at the secondary carbon in a 24 : 1 ratio. The reaction sequence can be successfully applied to a one-step synthesis of a carpenter bee sex pheromone starting from commercially available, optically pure (R)-(-)-2-hexanol and carbon monoxide. On the other hand, attempted reaction of a 1,2-diol type substrate resulted in beta-fragmentation rather than carbonylation. This suggests that for an application of this remote carbonylation to the synthesis of mevalonolactone, beta-hydroxy group should be introduced after constructing the key delta-lactone skeleton.
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