title: Palladium-Catalyzed Fluorination of Cyclic Vinyl Triflates: Effect of TESCF3as an Additive.
abstract: A method for the palladium-catalyzed fluorination of cyclic vinyl triflates has been developed. As with several previous palladium-catalyzed fluorination reactions using fluoride salts, controlling the regioselectivity presented a challenge in developing a practical synthetic procedure. The addition of triethyl(trifluoromethyl)silane (TESCF3) was found to effectively address this problem and resulted in drastically improved regioselectivities in this palladium-catalyzed fluorination reaction. This discovery, along with the use of a new biarylphosphine ligand, allowed for the development of an efficient and highly regioselective protocol for the fluorination of vinyl triflates. This method is compatible with a range of sensitive functional groups and provides access to five-, six-, and seven-membered cyclic vinyl fluorides.
authors.affiliation: Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
authors.forename: Yuxuan
authors.initials: Y
authors.lastname: Ye
authors.affiliation: Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
authors.forename: Takashi
authors.initials: T
authors.lastname: Takada
authors.affiliation: Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
authors.forename: Stephen L
authors.initials: SL
authors.lastname: Buchwald
mesh_terms: D002384:Catalysis; D003500:Cyclization; D054879:Halogenation; D008698:Mesylates / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D012821:Silanes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D008698:Mesylates; D012821:Silanes; D014753:Vinyl Compounds; C437735:vinyl triflate; D010165:Palladium
keywords: cross-coupling; fluorination; fluoroalkenes; palladium