Oxygenation vs iodonio substitution during the reactions of alkenyl-silanes with iodosylbenzene: participation of the internal oxy group.

Reaction of 4-acyl-oxy-but-1-enyl-silanes with iodosylbenzene in the presence of BF(3) x OEt(2) gave 4-acyloxy-2-oxobutyl-silane and 3-acyloxy-tetrahydrofuran-2-yl-silane via a 1,3-di-oxan-2-yl cation intermediate, which is generated by participation of the acyloxy group during the electrophilic addition of iodine(III) to the substrate.