title: Pi-pi stacking versus steric effects in stereoselectivity control: highly diastereoselective synthesis of syn-1,2-diarylpropylamines.
abstract: N-Arylarylideneamines react with sulfinylbenzyl carbanions derived from 2-(p-tolylsulfinyl)toluenes (S)-1 and (S)-2, affording epimeric mixtures at C1 of 1,2-diarylethyl- and 1,2-diarylpropylamine derivatives. The sulfinyl group completely controls the configuration at C2 in the reactions of (S)-2. The configuration at C1 depends on the electron density of the ring adjacent to the iminic carbon atom which is modulated by pi-pi stacking interactions with the ring joined to the carbanionic centre. The stereoselectivity was controlled by modifying the acceptor character of the arylideneamine ring with appropriate substituents, the formation of the highly selective (R) configuration at C1 being made possible by electron-donating groups. N-(2,4,6-Trimethoxyphenyl)arylideneamines have been shown to be suitable starting materials for the preparation of (R)-1,2-diarylethyl- and (1R,2S)-1,2-diarylpropylamines (syn epimers) in a highly stereoselective manner.
authors.affiliation: Departamento de Química Orgánica (C-I), Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain. joseluis.garcia.ruano@uam.es
authors.forename: José L
authors.initials: JL
authors.lastname: García Ruano
authors.forename: José
authors.initials: J
authors.lastname: Alemán
authors.forename: Inés
authors.initials: I
authors.lastname: Alonso
authors.forename: Alejandro
authors.initials: A
authors.lastname: Parra
authors.forename: Vanesa
authors.initials: V
authors.lastname: Marcos
authors.forename: José
authors.initials: J
authors.lastname: Aguirre
mesh_terms: D000588:Amines / Q000737:chemistry; D007097:Imines / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011437:Propylamines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry
chemical_list: D000588:Amines; D007097:Imines; D011437:Propylamines; D013455:Sulfur