title: Direct cupration of fluoroform.
abstract: We have found the first reaction of direct cupration of fluoroform, the most attractive CF(3) source for the introduction of the trifluoromethyl group into organic molecules. Treatment of CuX (X = Cl, Br, I) with 2 equiv of MOR (M = K, Na) in DMF or NMP produces novel alkoxycuprates that readily react with CF(3)H at room temperature and atmospheric pressure to give CuCF(3) derivatives. The CuCl and t-BuOK (1:2) combination provides best results, furnishing the CuCF(3) product within seconds in nearly quantitative yield. As demonstrated, neither CF(3)(-) nor CF(2) mediate the Cu-CF(3) bond formation, which accounts for its remarkably high selectivity. The fluoroform-derived CuCF(3) solutions can be efficiently stabilized with TREAT HF to produce CuCF(3) reagents that readily trifluoromethylate organic and inorganic electrophiles in the absence of additional ligands such as phenanthroline. A series of novel Cu(I) complexes have been structurally characterized, including K(DMF)[Cu(OBu-t)(2)] (1), Na(DMF)(2)[Cu(OBu-t)(2)] (2), [K(8)Cu(6)(OBu-t)(12)(DMF)(8)(I)](+) I(-) (3), and [Cu(4)(CF(3))(2)(C(OBu-t)(2))(2)(μ(3)-OBu-t)(2)] (7).
authors.affiliation: The Institute of Chemical Research of Catalonia (ICIQ), Tarragona 43007, Spain.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Zanardi
authors.forename: Maxim A
authors.initials: MA
authors.lastname: Novikov
authors.forename: Eddy
authors.initials: E
authors.lastname: Martin
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Grushin
mesh_terms: D005617:Chlorofluorocarbons, Methane / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D005617:Chlorofluorocarbons, Methane; D009942:Organometallic Compounds; D003300:Copper; C009554:fluoroform