title: Stereoselective quaternization of alpha-amino phenylacetonitriles mediated by a remote sulfinyl group.
abstract: Enantiomerically pure alpha-substituted alpha-amino phenylacetonitriles have been readily prepared from 2-p-tolylsulfinylbenzaldimines following a two-step sequence: a moderately stereoselective hydrocyanation of the imines and a completely stereoselective quaternization of the resulting diastereoisomeric mixture of alpha-amino phenylacetonitriles with different alkylating or acylating reagents in the presence of KHMDS. Theoretical calculations support a stereoselectivity control exerted by the remote sulfinyl group, as long as it is responsible for the conformational preferences of the benzyllithium intermediates, which suffer the attack of the electrophiles to the less hindered diastereotopic face.
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. joseluis.garcia.ruano@uam.es
authors.forename: José Luis García
authors.initials: JL
authors.lastname: Ruano
authors.forename: Ana M
authors.initials: AM
authors.lastname: Martín-Castro
authors.forename: Francisco
authors.initials: F
authors.lastname: Tato
authors.forename: Inés
authors.initials: I
authors.lastname: Alonso
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D000477:Alkylating Agents / Q000737:chemistry; D000838:Anions / Q000737:chemistry; D001554:Benzene / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods*; D008094:Lithium / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D011522:Protons; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry
chemical_list: D000097:Acetonitriles; D000477:Alkylating Agents; D000838:Anions; D011522:Protons; C006725:benzyl cyanide; D013455:Sulfur; D002244:Carbon; D008094:Lithium; D001554:Benzene; D010100:Oxygen