Hypervalent N-triflylimino-λ(3)-bromane undergoes direct and regioselective α-C-H amination of ethers at room temperature under transition metal-free conditions. Kinetic results, substituent and deuterium isotope effects suggest an asynchronous concerted organonitrenoid transition state with some hydride transfer character, analogous to that for alkane C-H insertions.

Oxidation of primary aliphatic aldehydes with p-trifluoromethylphenyl(difluoro)-λ(3)-bromane in dichloromethane at 0 °C afforded acid fluorides selectively in good yields, while that of aromatic aldehydes in chloroform at room temperature produced aryl difluoromethyl ethers. A larger migratory aptitude of aryl groups compared to primary alkyl groups during a 1,2-shift from carbon to an electron-deficient oxygen atom in bromane(III) Criegee-type intermediates will result in these differences in the reaction courses.

Exposure of 3-phenylpropyl ethers to an activated iodosylbenzene monomer·18-crown-6 complex [PhI(OH)BF(4)·18C6] in the presence of BF(3)-Et(2)O and water results in the para-selective monofluorination of benzene ring via neighboring alkoxy group participation and directly affords 3-(4-fluorophenyl)propyl ethers regioselectively in good yields.

Reaction of 3-phenylpropanol with an activated iodosylbenzene-18-crown-6 complex [PhI(OH)BF4-18C6] in dichloromethane in the presence of BF3-Et2O afforded directly the 6-chromanyl(phenyl)-lambda3-iodane-18C6 complex through tandem oxidative intramolecular cyclization yielding chroman and its regioselective phenyl-lambda3-iodanation.