Enantioselective Catalysis by Chiral Isothioureas

This review covers recent developments relating to organocatalyzed transformations by chiral isothioureas (ITUs) since their original introduction by Birman in 2006. This class of nucleophilic heterocycles was first involved in anhydride activation in enantioselective acyl transfer reactions, but it was more recently shown that activation of other reagents was possible, considerably enlarging their number of catalytic enantioselective transformations. Four main modes of activation as Lewis bases can currently be listed: (1) acylisothiouronium intermediates involved in acyl transfer, (2) silylisothiouronium species involved in silyl transfer, (3) acylisothiouronium enolates involved in several concerted and formal pericyclic transformations, and (4) α,β‐unsaturated acylisothiouronium species involved in domino transformations. This review is organized according to these different modes of activation of chiral isothioureas.