title: Synthesis of copper(I) complexes containing enantiopure pybox ligands. First assays on enantioselective synthesis of propargylamines catalyzed by isolated copper(I) complexes.
abstract: Dinuclear [Cu(2)(R-pybox)(2)][X](2) [X = PF(6), R-pybox = 2,6-bis[4'-(S)-isopropyloxazolin-2'-yl]pyridine (S,S)-(i)Pr-pybox (1), 2,6-bis[4'-(R)-phenyloxazolin-2'-yl]pyridine) (R,R)-Ph-pybox (2), 2,6-bis[4'-(S)-isopropyl-5',5'-difeniloxazolin-2'-yl]pyridine (S,S)-(i)Pr-pybox-diPh (3); X = OTf, (R,R)-Ph-pybox (4)] and mononuclear complexes [Cu(R-pybox)(2)][PF(6)] [R-pybox = (S,S)-(i)Pr-pybox (5), (R,R)-Ph-pybox (6)] have been diastereoselectively prepared by reaction of [Cu(MeCN)(4)][PF(6)] or CuOTf.0.5C(6)H(6) and the corresponding pybox ligand. The reaction of CuX (X = I, Br, Cl) with substituted pybox in a 2:1 molar ratio allows us to synthesize tetranuclear complexes [Cu(4)X(4)(R-pybox}(2)] [R-pybox = (S,S)-(i)Pr-pybox, X = I (7), Br (8); (R,R)-Ph-pybox, X = I (9), Br (10), Cl (11); (S,S)-(i)Pr-pybox-diPh, X = I (12), Cl (13)]. Dinuclear complexes [Cu(2)(mu-Cl)(R-pybox)(2)][CuCl(2)] [R-pybox = (S,S)-(i)Pr-pybox (15), (R,R)-Ph-pybox (16)] have been prepared by reaction of CuCl with (i)Pr-pybox or Ph-pybox in 3:2 molar ratio. The structures of the complexes 1, 2, 7, 15, 16 and that of the polymeric species [Cu(4)(mu(3)-Br)(3)(mu-Br)((i)Pr-pybox)](n) (14) have been determined by single-crystal X-ray diffraction analysis. Diffusion studies using (1)H and (19)F-DOSY experiments provide evidence that the different nuclearity of compounds 1 and 5 is maintained in the solution state and confirm that these ionic compounds exist in solution as stable, discrete, cationic complexes. The complexes 1-4, 6, 9, 10, and 16 as well as the previously reported [Cu(2){(S,S)-(i)Pr-pybox}(2)][OTf](2) have been assayed as catalysts in the enantioselective synthesis of propargylamines. The dinuclear complexes [Cu(2){(R,R)-Ph-pybox}(2)][X](2) (2, 4) were found to be the most efficient catalysts (up to 89% e.e.).
authors.affiliation: Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica Enrique Moles (Unidad Asociada al C.S.I.C.), Universidad de Oviedo, 33071 Oviedo, Principado de Asturias, Spain.
authors.forename: María
authors.initials: M
authors.lastname: Panera
authors.forename: Josefina
authors.initials: J
authors.lastname: Díez
authors.forename: Isabel
authors.initials: I
authors.lastname: Merino
authors.forename: Eduardo
authors.initials: E
authors.lastname: Rubio
authors.forename: M Pilar
authors.initials: MP
authors.lastname: Gamasa