Аннотация:A novel access to isoxazolines was developed using the [4+1]‐annulation of α‐keto‐stabilized sulfur ylides with N,N‐bis(siloxy)enamines derived from aliphatic nitro compounds. The resulting 5‐keto‐substituted isoxazolines were shown to be convenient precursors of polysubstituted 3‐hydroxypyrrolidines via the one‐pot catalytic N‐O hydrogenolysis/intramolecular reductive amination sequence. Application of this approach to the formal synthesis of Merck’s potent NK1 receptor antagonist was demonstrated.