SYNTHESIS AND REACTIONS OF STABLE ALKOXYARYLTRIFLUOROPERIODINANES - TAMED ANALOG OF IODINE PENTAFLUORIDE FOR USE IN OXIDATIONS OF AMINES, ALCOHOLS, AND OTHER SPECIES

Stable alkoxyaryltrifluoroperiodinanes 2 and 5 were prepared by oxidation of the respective parent iodo alcohols (1 and 4) with excess trifluoromethyl hypofluorite. The stability and low reactivity of 2 and 5 are ascribed to the strong stabilizing influence of the five-membered ring. The reaction of 2 with trimethylsilyl chloride gives the corresponding iodine(lll) species, chloroalkoxyaryliodinane 3, and chlorine. Compound 2 is hydrolyzed with aqueous base to give a species thought to be iodinane oxide 6a. Periodinane 2 has been demonstrated, by small-scale exploratory reactions, to be a selective reagent for the oxidation of primary and secondary amines or alcohols bearing α hydrogens to the corresponding aldehyde or ketone. In contrast to iodine pentafluoride, 2 does not further oxidize the product aldehydes to acids, tert-Butylamine is oxidized by 2 to give 1, 1, 1', 1'- tetramethylazoethane. Phenylmagnesium bromide reacts with 2 to give fluorobenzene. Possible mechanisms for these selective oxidations are discussed. It is suggested that the stabilizing structural features of 2 make it a “tamed” analogue of 1F5. © 1979, American Chemical Society. All rights reserved.