International audienceThis 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,_-unsaturated acylisothiouronium species involved in domino transformations. This review is organized according to these different modes of activation of chiral isothioureas

The development of efficient catalytic asymmetric methodologies for the construction of chiral, nonracemic tertiary alcohols is currently a challenging research area of interest, [1] and a few asymmetric catalytic methods dealing with this demanding task have been described. [2][3][4][5][6][7] Despite excellent progress in the field of metal-catalyzed enantioselective nucleophilic addition to ketones, only limited success has

Asymmetric catalysis provides outstanding tools to introduce chiral information to a substrate by using only catalytic amounts of a chiral transition-metal complex.[1] The success of these efficient asymmetric processes relies on the development of chiral ligands that form a complex with the metal; until very recently phosphorus-, nitrogen-, and oxygen-containing chiral ligands were the only ones available. Recently, the groups of Hayashi and Carreira independently reported the use of chiral dienes in asymmetric catalysis: [2] high levels of enantioselectivity were achieved in both the iridiumcatalyzed kinetic resolution of allyl carbonates [3] and the rhodium-catalyzed 1,4-additions of organoboron reagents to Michael acceptors. [4,5]