Halogen‐Atom‐Transfer Enabled Radical Fluoroalkyl‐Thiolation of Unactivated Alkenes

We develop a halogen atom transfer‐enabled radical fluoroalkyl‐thiolation of unactivated alkenes employing fluoroalkyl iodides, TMEDA‐ligated zinc thiolates. Notably, the aryldiazonium salts were utilized as the promoter in the three‐component reaction, providing a powerful tool for simultaneous construction of CRf and CS bonds across the CC bond. Moreover, direct thiolation of fluoroalkyl iodides without alkene gives the two‐component reaction products. Mechanistic studies supported that the interaction between diazonium salt and zinc thiolate plays a crucial role in the transformations.