Chiral γ‐Amino Amide Synthesis by Heterobimetallic Lanthanum/Lithium/Pybox‐Catalyzed Direct Asymmetric Mannich‐Type Reactions of α‐Keto Anilides

Not so Mannich now: A heterobimetallic La/Li/pybox complex was key in direct catalytic asymmetric Mannich-type reactions, using α-keto anilides as synthetic homoenolate equivalents to afford γ-amino amide products in up to >99 % yield, 95 % ee, and >97:3 syn-selectivity. Stereoselective reduction of the α-keto moiety afforded the β-alkyl-γ-amino-α-hydroxy amide with three contiguous stereocenters (PG=protecting group).