An enantioconvergent halogenophilic nucleophilic substitution (S N 2X) reaction

Abstract

Attack from the front Biomolecular substitution reactions are widely applied to compounds with carbon-halogen bonds. Typically, an incoming reactive group will attack the carbon from behind its bond with the halogen, causing the halogen to depart in the opposite direction. Zhang et al. now present an asymmetric catalytic substitution reaction that flips the script with an attack on the halogen from the front. Specifically, nitrogen and sulfur nucleophiles stripped bromine from a variety of carbon centers activated by electron-withdrawing groups. A chiral cationic catalyst then directed the carbon fragment back to form a carbon-sulfur or carbon-nitrogen bond enantioselectively. Science , this issue p. 400