Enantioselective synthesis of monofluorinated allylic compounds: Pd-catalyzed asymmetric allylations of dimethyl 2-fluoromalonate using new N-sulfinyl-based ligands

Abstract

New chiral S,N- and S,P-ligands starting from tert-butanesulfinamide were synthesized in four steps, applying Pd-catalyzed asymmetric allylic substitutions of dimethyl 2-fluoromalonate. The induced effect of the Pd/S,N-ligand catalyst on the enantioselectivity depends on the steric demand of the substituent at the o-position of the pyridine ring. This method produced monofluorinated allylation products in up to high yield with high enantioselectivity.