Direct Intermolecular Anti-Markovnikov Hydroazidation of Unactivated Olefins

We herein report a direct intermolecular
anti-Markovnikov hydroazidation
method for unactivated olefins, which is promoted by a catalytic amount
of bench-stable benziodoxole at ambient temperature. This method facilitates
previously difficult, direct addition of hydrazoic acid across a wide
variety of unactivated olefins in both complex molecules and unfunctionalized
commodity chemicals. It conveniently fills a synthetic chemistry gap
of existing olefin hydroazidation procedures, and thereby provides
a valuable tool for azido-group labeling in organic synthesis and
chemical biology studies.