Remote Radical Azidation of Unactivated C(sp3)–H Bonds in Sulfamoyl Azides

An efficient method for remote radical C­(sp3)–H azidation at unactivated sites is described. C–H functionalization proceeds via intramolecular 1,5-hydrogen atom transfer to N-centered radicals that are generated via azido group transfer and/or fragmentation. The readily installed sulfamoyl azide serves as both an amidyl radical precursor and an azido source. This reaction features excellent site selectivity for tertiary, secondary, primary, and benzylic C­(sp3)–H bonds and exhibits broad functional group compatibility.