Safe and Controllable Azidochlorination of Olefins With in Situ Generated Chlorine Azide

ABSTRACT A safe and rapid one‐pot synthesis of azidochlorides with cheap and readily available raw materials without any catalyst is reported. This method utilizes stable and nonexplosive TMSN 3 as an azide source, which reacts with sodium hypochlorite in the presence of acetic acid to deliver ClN 3 . The in situ generated ClN 3 then reacts with olefins to give the difunctionalized azidochlorides with exclusive regioselectivity, yielding 25 diverse products in 43%–93% yields. Their synthetic application was demonstrated by converting to a variety of 1,2,3‐triazoles with high yields (24 examples).