Mechanistic studies of the free-radical fragmentation of monoalkyl diazenes

Article abstract of DOI:10.1016/S0040-4039(97)01497-4

Mechanistic studies of the deoxygenation of primary alcohols by Mitsumobu displacement with o-nitrobenzenesulfonylhydrazine (NBSH) reveal that the monoalkyl diazene intermediates formed in this process are exceedingly good hydrogen-atom donors toward alkyl radicals, exceeding tri-n-butylin hydride in reactivity. Competition experiments are described wherein the radical intermediates are trapped by intra- and intermediate addition to carbon-carbon double bonds, to dioxygen, and to the free radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO).