| Project/Area Number |
60570986
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | Kyoto University |
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Principal Investigator |
OCHIAI Masahito Institute for Chemical Research, Kyoto University, 化学研究所, 助手 (50127065)
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| Project Period (FY) |
1985 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1986: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1985: ¥1,100,000 (Direct Cost: ¥1,100,000)
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| Keywords | hypervalent organoiodine compound / iodosylbenzene / oxidative 1,4-fragmentation / <gamma> -stannyl alcohol / medium-sized lactone / ハイパーバレント相互作用 |
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| Research Abstract |
Recently, we developed a new and efficient ring opening reaction of carbocycles that yields unsaturated carbonyl compounds by iodine( <III> )-mediated oxidative 1,4-fragmentation of <gamma> -tributylstannyl alcohols. We have now examined the stereochemical course of the fragmentation reaction. The oxidative 1,4-fragmentation was found to proceed in a completely stereospecific manner and applied to the stereoselective synthesis of the mosquito pheromone, erythro-6-acetoxyhexadecan-5-olide. Furthermore, a new ring expansion route to olefinic lactones was developed. Oxidative 1,4-fragmentation of tributylstannyl lactols utilizing (diacetoxyiodo)benzece under mild conditions gave unsaturated medium-ring lactones stereosepecifically in good yields. The relative stereochemistry of tributylstannyl group of the lactols determines the double bond geometry of the lactones. We also found unambiguous evidence indicating the fixation of molecular geometry of cis-1,3-disubstituted cyclohexanes to the diaxial conformer by the intramolecular hypervalent interaction between tin and etheric oxygen atoms. The "stabilizing 1,3-diaxial interaction" results in the highly stereoselective osmylation for double bonds with production of vicinal glycols.
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