title: Alpha-bromo-alpha,alpha-difluoroallyl derivatives as synthetic intermediate: nucleophilic substitution of alpha-bromo-alpha,alpha-difluoroallyl derivatives in the presence of palladium catalysts.
abstract: The palladium catalyzed nucleophilic substitution of alpha-bromo-alpha,alpha-difluoroallyl derivatives turned out to be an efficient method for the preparation of several fluorinated organic molecules. Several soft carbon nucleophiles regioselectively reacted with 3-bromo-3,3-difluoropropene (BDFP) to give the 3-substituted 1,1-difluoroalkenes. Phenylzinc chloride and tributylphenyltin afforded 1-fluoro-1,3-diphenylpropene. The radical bromination of 3-substituted 1,1-difluoroalkenes provided 1-substituted BDFPs, and a 1-substituted BDFP reacted with carbon nucleophiles to give 1,3-disubstituted 3,3-difluoroalkenes. For the reaction of nitrogen nucleophiles with BDFP, an amine and the sodium salts of the carbamates reacted with BDFP at the gamma-position. However, the sodium salts of the sulfoneamide predominantly attacked at the alpha-position.
authors.affiliation: Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, Sugitani, Japan. kirihara@ms.toyama-mpu.ac.jp
authors.forename: M
authors.initials: M
authors.lastname: Kirihara
authors.forename: T
authors.initials: T
authors.lastname: Takuwa
authors.forename: M
authors.initials: M
authors.lastname: Okumura
authors.forename: T
authors.initials: T
authors.lastname: Wakikawa
authors.forename: H
authors.initials: H
authors.lastname: Takahata
authors.forename: T
authors.initials: T
authors.lastname: Momose
authors.forename: Y
authors.initials: Y
authors.lastname: Takeuchi
authors.forename: H
authors.initials: H
authors.lastname: Nemoto
mesh_terms: D002384:Catalysis; D017611:Fluorine Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010165:Palladium / Q000737:chemistry*
chemical_list: D017611:Fluorine Compounds; D010165:Palladium