Studies on Synthetic Organic Reactions Using Iodobenzene Dicarboxylate

铊（III）、汞（II）和铅（IV）盐是有机合成中非常有用的试剂。然而，由于这些试剂的高毒性，使用这些金属盐的反应不适合工业生产。我们发现用二羧酸碘苯（PhI(OCOR)2' 1）代替上述试剂可以进行以下反应（1-4）。1)用二醋酸碘苯（la）影响了3-芳基丙酸向2-芳基琥珀酸的1,2-芳基迁移。该迁移成功地应用于制备具有抗炎活性的吲哚-1-羧酸的重要合成中间体- 2-芳基琥珀酸。2)以二氟乙酸碘苯（lb）为原料，实现了乙基甲醇基短而高效地转化为二羟基丙酮基。该转化成功地应用于阿霉素（抗肿瘤剂）和皮质类固醇（抗炎剂）的二羟丙酮侧链的合成。3)用lb试剂处理< α > -酰基硫化物得到与< α > -酰基亚砜的Pummerer反应相同的产物。该反应成功地应用于碳碳键形成反应，如Friedel-Crafts型环化反应和烯烃环化反应。4) < β > -取代< α >, < β > -不饱和羰基化合物与试剂la在基本反应条件下反应得到< α > '-羟基- < α >, < β > -不饱和羰基化合物。< β > -非取代< α >, < β > -不饱和羰基化合物的相同反应产生< α > -羟基- < β > -甲氧基二甲基缩醛化合物。5)在上述反应（1-4）中，试剂1被回收为碘苯，通过二氯化碘成功转化为试剂1。因此，试剂1可以循环使用。

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.