Application of PhSCF2CF2SiMe3 as a Tandem Anion and Radical Tetrafluoroethylene Equivalent: Fluoride-Catalyzed Addition to N-Substituted Cyclic Imides Followed by Radical Cyclization

PhSCF2CF2SiMe3 undergoes a fluoride-catalyzed nucleophilic addition to N-substituted cyclic amides affording adducts in moderate to good yields. Reductive cleavage of the phenylsulfanyl group of N-methylated adducts under radical conditions yields the corresponding tetrafluoroethyl-containing adducts in excellent yields. Under the same reduction conditions, N-allylated adducts undergo 6-exo radical cyclization to afford the corresponding tetrafluorinated 1-azabicyclic compounds in moderate to good yields and cis selectivities.