Scheme 1. On demand generation of NCF3(PG) anions and their reaction with electrophiles. All yields are those of isolated compounds. Standard conditions for [NCF3(PG)] -generation: imidoyl dichloride derivative (0.1 M in MeCN with 1 equiv of 18-crown-6) was passed through a 3.8 mL cartridge filled with a 7:3 w/w mixture of CsF and glass beads. Standard conditions for the substitution: electrophile (0.2 mmol) is added to the solution of the anion (from 2 to 4 equivalents) and heated at 80 ºC. For detailed reaction conditions of each substrate see the S.I. a 1.1 equiv of AgOTf were used. b Isolated after an esterification step. c Isolated after bromination of the BPin moiety. d 3-substituted benzyl bromide was used e From the bromide. f Reaction performed in batch. g From the iodide.