title: On accounting for the stereoselective control of the metal-catalyzed Rautenstrauch cyclopropanation by computational methods.
abstract: The mechanism of the intramolecular Pt(II)-catalyzed Rautenstrauch cyclopropanation and the stereochemical implications have been investigated by computational methods. The reaction takes place through a cyclopropanation step preceding the cleavage of the C-O bond, thus ensuring the transfer of chiral information from the stereogenic propargylic center. Our results agree with experimental findings and account for the origin of the substrate-dependent selectivity on the basis of subtle electronic effects and steric interactions in the cyclopropanation transition-state structure.
authors.affiliation: Laboratorio de Resonancia Magnética, Instituto de Investigaciones Biomédicas (CSIC), C/ Arturo Duperier 4, 28029-Madrid, Spain. esoriano@iib.uam.es
authors.forename: Elena
authors.initials: E
authors.lastname: Soriano
authors.forename: José
authors.initials: J
authors.lastname: Marco-Contelles
mesh_terms: D002384:Catalysis; D003201:Computers; D003521:Cyclopropanes / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D003521:Cyclopropanes; D008670:Metals