Late‐Stage Dehydroxyazidation of Alcohols Promoted by Trifunctional Hypervalent Azido‐Iodine(III) Reagents

The development of convenient new methods for the synthesis of organic azides is highly desirable. Herein, we report a practical method for dehydroxyazidation of alcohols via an SN2 pathway involving PPh3 and trifunctional benziodazolone‐based hypervalent azido‐iodine(III) reagents, which function as an electrophilic center, an azido source, and a base. This mild, chemoselective method was used for late‐stage azidation of structurally complex alcohols, as well as for a new synthetic route to the antiepileptic drug rufinamide. The reaction mechanism was also investigated both experimentally and computationally. We developed a mild, metal‐free practical method for late‐stage dehydroxyazidation of structurally complex alcohols promoted by trifunctional hypervalent azido‐iodine(III) reagents ABZ. The reactions proceeded via an SN2 pathway and showed excellent chemoselectivity and stereospecificity and gave the corresponding azides in high yields. The reaction mechanism was investigated by means of experiments and DFT calculations.