Chemoselective Csp²‐H Radical Alkylation of Aryl Diazonium Salts with 1‐Iodo‐3‐Pentafluorosulfanylbicyclo[1,1,1]pentane (<scp>SF5</scp>‐<scp>BCP</scp>‐I)^†

Comprehensive Summary The reaction site of aryl diazonium salt was restricted in the position of diazonium moiety, due to the intrinsic electrophilicity of diazonium moiety. Herein, we described an unprecedented chemoselective alkylation of Csp 2 ‐H of aryl diazonium salts with 1‐iodo‐3‐pentafluorosulfanylbicyclo[1,1,1]pentane (SF 5 ‐BCP‐I). This novel alkylation of aryl diazonium salts provided an efficient access to various SF 5 ‐BCP substituted aromatics that might have great potential application in the drug discovery. Mechanistic experiments and theoretical studies revealed that the intrinsic electrophilic SF 5 ‐BCP radical resulted in the thermodynamic favorable radical addition on Csp 2 ‐H site rather than diazonium moiety of aryl diazonium salt.