SYNTHESIS AND REACTION OF SUBSTITUTED ARYLALKOXYIODINANES - FORMATION OF STABLE BROMOARYLALKOXY AND ARYLDIALKOXY HETEROCYCLIC-DERIVATIVES OF TRICOORDINATE ORGANOIODINE(III)

The first stable, crystalline bromoiodinanes, 1a and 2a, as well as the first aryldialkoxyiodinanes, have been synthesized from the respective alcohols 4 and 5. Two chloroiodinanes, 1b and 2b, have been prepared by chlorination of the parent alcohols. Bromo-and chloroiodinanes have been shown to be synthetically useful as highly selective, free-radical halogenating agents for benzylic and allylic hydrogens. Reactivity patterns of these species differ sufficiently from those evidenced by other iodine(III) species, to suggest a possible niche for these compounds in synthetic organic chemistry. Treatment of either lb or 2b with potassium hexafluorocumyl oxide (KORF) gives the respective dialkoxy species 8 or 9. Degenerate ligand exchange for either 8 or 9 occurs rapidly on the NMR time scale with 0.08-0.10 M KORF(T8= 56 °C, T9= 93 °C), but not with a comparable concentration of RFOH, suggesting an associative exchange mechanism. © 1979, American Chemical Society. All rights reserved.