Palladium-catalyzed allylic substitution of secondary allylic esters with ketone enolates

Palladium-catalyzed allylic substitution of unsymmetrically substituted secondary allylic esters with eight enolate anions derived from ketones and an ester was examined to find that the substitution of the phosphate esters with lithium enolates proceeded regioselectively. The stereochemical course of the substitution was studied using enantiomerically enriched allylic phosphate to confirm retention of the stereochemistry. The cyclic version of the allylic phosphate afforded substitution products with the same sense of the regio- and stereoselectivity. (C) 2015 Elsevier Ltd. All rights reserved.