title: Direct synthesis of α-trifluoromethyl ketone from (hetero)arylacetylene: design, intermediate trapping, and mechanistic investigations.
abstract: Regioselective addition across the alkynes has been achieved in a silver-catalyzed protocol utilizing Langlois reagent (CF3SO2Na) and molecular O2 to access medicinally active α-trifluoromethyl ketone compounds. This method was successful in producing α-trifluoromethyl ketone in heterocyclic scaffolds, which are incompatible with earlier strategies. Experimental findings suggest a mechanism involving α-styrenyl radical intermediate and 1-methyl-2-pyrrolidinone (NMP) solvent, which leads to crystallographically characterized N-methylsuccinimide. Isotope labeling, kinetic studies, and intermediate trapping further helped to gain insight into this energy-demanding process.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
authors.forename: Arun
authors.initials: A
authors.lastname: Maji
authors.forename: Avijit
authors.initials: A
authors.lastname: Hazra
authors.forename: Debabrata
authors.initials: D
authors.lastname: Maiti
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D011760:Pyrrolidinones / Q000737:chemistry; D012997:Solvents; D013237:Stereoisomerism; D013388:Succinimides / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D000480:Alkynes; D007659:Ketones; C110990:N-methylsuccinimide; D011760:Pyrrolidinones; D012997:Solvents; D013388:Succinimides; C038678:N-methylpyrrolidone