A novel Pd/sulfoxide catalyzed diastereoselective allylic C-H amination reaction of chiral homoallylic N-tosyl carbamates is reported. Densely oxygenated alpha-olefin substrates with multiple stereogenic centers undergo allylic C-H amination in excellent yields and with diastereoselectivities that are controlled by the stereocenter that bears the N-tosyl carbamate. Streamlined routes to stereochemically defined anti-oxazolidinones that can be further elaborated to medicinally and biologically relevant 1,2-amino alcohols are also demonstrated. Evidence is provided that this reaction proceeds via a Pd/sulfoxide-mediated allylic C-H cleavage to form a pi-allylPd intermediate followed by Pd(II) counterion-assisted deprotonation of the nitrogen nucleophile to effect functionalization.