title: Dimethylzinc-Mediated Addition of Phenylacetylene to α-Diketones Catalyzed by Chiral Perhydro-1,3-benzoxazines.
abstract: An efficient, enantioselective Me2Zn-mediated monoaddition of phenylacetylene to α-diketones in the presence of a chiral perhydro-1,3-benzoxazine ligand is described. At temperatures higher than -20 °C, a kinetic resolution of the resulting α-hydroxy ketone occurs, which greatly improves the enantioselectivity although with moderate chemical yield. The alkynylation of nonsymmetrical aromatic diketones with electronically different substituents on the aromatic rings proceed with high regioselectivity. This procedure allows the preparation of α-hydroxy-α-ynyl ketones as highly enantioenriched materials.
authors.affiliation: Instituto CINQUIMA and Departamento de Química Orgánica, Facultad de Ciencias and ‡Instituto CINQUIMA and Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid , Paseo de Belén, 7, 47011 Valladolid, Spain.
authors.forename: Rebeca
authors.initials: R
authors.lastname: Infante
authors.affiliation: Instituto CINQUIMA and Departamento de Química Orgánica, Facultad de Ciencias and ‡Instituto CINQUIMA and Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid , Paseo de Belén, 7, 47011 Valladolid, Spain.
authors.forename: Jose M
authors.initials: JM
authors.lastname: Martin-Alvarez
authors.affiliation: Instituto CINQUIMA and Departamento de Química Orgánica, Facultad de Ciencias and ‡Instituto CINQUIMA and Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid , Paseo de Belén, 7, 47011 Valladolid, Spain.
authors.forename: Celia
authors.initials: C
authors.lastname: Andrés
authors.affiliation: Instituto CINQUIMA and Departamento de Química Orgánica, Facultad de Ciencias and ‡Instituto CINQUIMA and Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid , Paseo de Belén, 7, 47011 Valladolid, Spain.
authors.forename: Javier
authors.identifier: 0000-0002-5655-3320
authors.initials: J
authors.lastname: Nieto