Double amination of 2-fluoroallylic acetates by palladium catalysts

Abstract

We accomplished the palladium-catalyzed double substitution of 2-haloallylic acetates with nitrogen nucleophiles. During the Pd2(dba)3/DPPE-catalyzed reaction of 2-fluoroallylic acetates with N-substituted-p-toluenesulfonamide, two equivalents of nitrogen nucleophiles were introduced to the allyl unit with a Z-selectivity through the carbon–fluorine bond cleavage. We further demonstrated the reaction of 2-chloroallylic acetates, and succeeded in obtaining the same doubly-substituted products in good yields with a high Z-selectivity.