1985 Fiscal Year Final Research Report Summary
Studies on Synthetic Organic Reactions Using Iodobenzene Dicarboxylate
| Project/Area Number |
59870070
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | Osaka University |
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Principal Investigator |
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| Project Period (FY) |
1984 – 1985
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| Keywords | hypervalent iodine compound / iodobenzene diacetate / iodobenzene ditrifluoroacetate / 1,2-aryl migration / 2-arylsuccinic acid / Pummerertype reaction / dihydroxyacetone group |
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| Research Abstract |
Thallium(III), mercury(II) and lead(IV) salts are very useful reagents in organic syntheses. However, the reactions using these metalic salts are unsuitable for industrial production because of high toxicity of these reagents. We have found that the following reactions(1-4) can be carried out using iodobenzene dicarboxylate (PhI(OCOR)2' 1) in place of the above reagents.
1) The 1,2-aryl migration of 3-aroylpropionic acid to 2-arylsuccinate was effected by using iodobenzene diacetate(la). The migration was successfully applied to the preparation of 2-arylsuccinic acid which is important synthetic intermediate for indan-1-carboxylic acid possessing antiinflammatory activity.
2) The short and efficient conversion of ethynylcarbinol groups into dihydroxyacetone groups was achieved by using iodobenzene ditrifluoroacetate (lb). The conversion was successfully applied to the syntheses of dihydroxyacetone side chains of adriamycin(antitumor agent) and cortico steroid(antiinflammatory agent).
3) Treatment of <alpha> -acylsulfides with the reagent lb gave the same products as obtained by the Pummerer reaction of <alpha> -acylsulfoxides. The reaction was successfully applied to the carbon-carbon bond forming reactions such as Friedel-Crafts type cyclization and olefin cyclization.
4) The reaction of <beta> -substituted <alpha> , <beta> -unsaturated carbonyl compound with the reagent la under basic reaction conditions gave <alpha> '-hydroxy- <alpha> , <beta> -unsaturated carbonyl compound. The same reaction of <beta> -nonsubstituted <alpha> , <beta> -unsaturated carbonyl compound afforded <alpha> -hydroxy- <beta> -methoxydimethylacetal compound.
5) In the above reactions(1-4), the reagent 1 was recovered as iodobenzene, which was successfully converted into the reagent 1 through iodobenzene dichloride. Consequently, the reagent 1 can be recycled.
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