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Stereoselective Quaternization of α-Amino Phenylacetonitriles Mediated by a Remote Sulfinyl Group

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posted on 03.08.2007, 00:00 by José Luis García Ruano, Ana M. Martín-Castro, Francisco Tato, Inés Alonso
Enantiomerically pure α-substituted α-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 α-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.