High yielding and highly diastereoselective methods for I,2-additions of organometallic reagents to N-tert-butanesulfinyl aldimines (2) and N-tert-butanesulfinyl ketimines (3) are described. The additions of alkyl, aryl, alkenyl, and allyl carbanions to a diverse set of imines with different steric and electronic properties are demonstrated. Acidic methanolysis of the sulfinamide products (4 and 6) delivers highly enantioenriched alpha-branched and alpha,alpha-dibranched amines. Since a broad range of sulfinyl imines are easily accessible from aldehydes and ketones, a wide variety of enantioentriched amines may be prepared. (C) 1999 Elsevier Science Ltd. All rights reserved.