Significance: Addition of enantiomerically pure sulfinimine anions to N-sulfonyl aldimines gave the addition product with excellent diastereoselectivity. The E-sulfonylimine is much more reactive than the Z-sulfonylimine, possibly due to the increased steric hinderance in the transition state of the Zsulfonylimine. The single diastereoisomer obtained can be rationalized by the steric bulk and orientation of the tert-butylsulfonyl group.Comment: The aza variant of the Mannich reaction whereby an enamide anion reacts with an imine to give a-amino imine has not been well explored due to the general instability of the carbonnitrogen bond. Recently, the development of a sulfinimine methodology circumvented this problem and also allowed the possibility of stereocontrol by use of the chiral sulfur center. The reaction reported by Lanter is highly diastereoselective for both alkyl-and aryl-substituted sulfinimines. Application of this methodology to the synthesis of a bromopyrrole alkaloid is also described. N R 1 S Ot-Bu N R 2 SO 2 t-Bu N R 1 S O t-Bu R 2 N H t-BuO 2 S LiHMDS THF, -78 °C 16 examples 50-93% yield 60-98% de R 1 , R 2 = Ar, Hetar, Alk

This paper reports the desymmetrization of cyclohexadienones through stereoselective intramolecular aza-Michael addition with a tethered chiral sulfinamide nucleophile. The reaction was facilitated by phase-transfer catalysis and produced various nitrogen-containing bicyclic compounds with a yield of up to 93% and a diastereomeric ratio of up to >20:1.