One-Pot Synthesis of Fluoroalkanesulfonyl Substituted Amidines from Ketone, Amine and Fluoroalkanesulfonyl Azides in Mild Conditions

Abstract

A facile one-step method is presented for the synthesis of N-per(poly)fluoroalkanesulfonyl amidines in moderate to good yield by reactions of per(poly)fluoroalkanesulfonyl azides, ketone and secondary amine at room temperature. This synthetic methods provide an easy and simple access to N-per(poly)fluoroalkanesulfonyl amidines.

Trifluoromethanesulfonamides and Related Compounds

“…The same compounds were synthesized by the CF-catalyzed reaction of N-trimethylsilylated nonafluorobutanesulfonamide C 4 F 9 SO 2 NHSiMe 3 with dimethylformamide, 134 or by the reaction of perfluoroalkanesulfonylazides with ketones and secondary amines. 135 The simplest representative, N-[(dimethylamino)methylidene]triflamide CF 3 SO 2 NCHNMe 2 , was obtained in 94% yield by the reaction of 2-phenyl-2H-1,2,3-triazol-4ylcarbonyl chloride with the sodium salt of triflamide in DMF. 136 The mechanism apparently includes the formation of the "Vilsmeier-type" adduct of acyl chloride with DMF, which further reacts with the triflamide salt with regeneration of 2phenyl-2H-1,2,3-triazol-4-yl carboxylic acid.…”

“…149,154,155 Three-component reaction of perfluoroalkanesulfonylazides with ketones and secondary amines was proposed as a one-pot synthesis of fluorinated amidines. 135,156 Amidines of the same structure but with other substituents at the central carbon atom were obtained by the copper(I)-catalyzed one-pot, three-component reaction of perfluoroalkanesulfonylazides with 1-alkynes and secondary amines. 157 A similar reaction with iminophosphoranes instead of secondary amines gives rise to N-fluoroalkanesulfonylphos-phorous amidines.…”

Encyclopedia of Reagents for Organic Synthesis

“…β-Ketoester enamines suffer a cleavage (eq 23). 34 Acyclic ketones give rearranged amidines 16 under the same conditions (eq 24). Reaction time and product yield vary broadly with the nature of the secondary amine, the starting ketone and the addition of molecular sieves.…”

Basicity of trifluoromethylsulfonylformamidines. DFT and FTIR study and NBO analysis

“…N ‐Sulfonylamidines are useful synthetic intermediates and efficient coordinating ligands, and the RSO 2 NC―NR′ 2 motif is present in many bioactive natural products and pharmacophores . In most cases they are the derivatives of arenesulfonamides, whereas fluorine‐containing sulfonylamidines, in spite of their unique and specific structure, are much less studied both synthetically and theoretically . The presence of several centers of basicity in the molecules of N ‐sulfonylamidines makes them interesting objects for spectroscopic and theoretical investigation.…”