title: New preparation and synthetic reactions of 3,3,3-trifluoropropynyllithium, -borate and -stannane: facile synthesis of trifluoromethylated allenes, arylacetylenes and enynes.
abstract: BACKGROUND
  Since trifluoromethyl-containing compounds have found diverse applications in the fields of pharmaceuticals and agrochemicals, facile and selective synthetic methods for trifluoromethyl-substituted compounds are an essential tool for advanced medicinal chemistry. Now that diverse synthetic transformations of carbon-carbon triple bonds are available, 3,3,3-trifluoropropynyl-substituted compounds serve as versatile building blocks for target molecules containing trifluoromethyl groups. Thus, novel synthetic methods and reagents for incorporation of a 3,3,3-trifluoropropynyl group into an organic compound have been the major concern in exploration and modification of fluorine-based biologically active substances.
  
  
  CONCLUSIONS
  We report a preparative method of 3,3,3-trifluoropropynyllithium and its reaction with electrophiles including aldehydes, ketones, trimethoxyborane, chlorosilanes and chlorostannanes in detail. Palladium-catalyzed synthetic reactions of the carbonyl adducts and the trifluoromethyl-containing metalloid reagents are also demonstrated, which provide simple synthetic methods of trifluoromethylated allenes, arylacetylenes and enynes. The synthetic transformations presented here expand the repertoire of trifluoromethylated compounds available for medicinal scientists and contribute to the advance of future medicinal chemistry.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan. m.shimizu@hs2.ecs.kyoto-u.ac.jp
authors.forename: Masaki
authors.initials: M
authors.lastname: Shimizu
authors.forename: Masahiro
authors.initials: M
authors.lastname: Higashi
authors.forename: Youhei
authors.initials: Y
authors.lastname: Takeda
authors.forename: Masahito
authors.initials: M
authors.lastname: Murai
authors.forename: Guofang
authors.initials: G
authors.lastname: Jiang
authors.forename: Yuiga
authors.initials: Y
authors.lastname: Asai
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Nakao
authors.forename: Eiji
authors.initials: E
authors.lastname: Shirakawa
authors.forename: Tamejiro
authors.initials: T
authors.lastname: Hiyama
mesh_terms: D000114:Acetylene / Q000737:chemistry*; D000466:Alkadienes / Q000737:chemistry*; D001881:Borates / Q000737:chemistry*; D002384:Catalysis; D005461:Fluorine / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D013451:Sulfonic Acids / Q000737:chemistry; D017971:Tin Compounds / Q000737:chemistry*
chemical_list: D000466:Alkadienes; D001881:Borates; D009942:Organometallic Compounds; D013451:Sulfonic Acids; D017971:Tin Compounds; C031525:stannane; D005461:Fluorine; C025947:propadiene; D010165:Palladium; D000114:Acetylene