title: Chiral sulfoxides in the enantioselective allylation of aldehydes with allyltrichlorosilane: a kinetic study.
abstract: The mechanism of the allylation of aldehydes in the presence of allyltrichlorosilane employing the commercially available (R)-methyl p-tolyl sulfoxide as a Lewis base has been investigated. The combination of kinetic measurements, conductivity analysis and quantum chemical calculations indicates that the reaction proceeds through a dissociative pathway in which an octahedral cationic complex with two sulfoxides is involved. The lack of turnover is ascribed to the formation of neutral sulfurane derivatives.
authors.affiliation: Dipartimento di Chimica e Biologia, Università di Salerno, Via Ponte Don Melillo, 84084 - Fisciano, SA, Italy. gmonaco@unisa.it
authors.forename: Guglielmo
authors.initials: G
authors.lastname: Monaco
authors.forename: Chiara
authors.initials: C
authors.lastname: Vignes
authors.forename: Francesco
authors.initials: F
authors.lastname: De Piano
authors.forename: Assunta
authors.initials: A
authors.lastname: Bosco
authors.forename: Antonio
authors.initials: A
authors.lastname: Massa
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D055601:Organic Chemistry Phenomena; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism; D013454:Sulfoxides / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D000475:Alkenes; D012821:Silanes; D013454:Sulfoxides; C516132:allyltrichlorosilane