Double diastereocontrol in bifunctional thiourea organocatalysis: iterative Michael-Michael-Henry sequence regulated by the configuration of chiral catalysts.

The importance and reactivity consequences of the double diastereocontrol in noncovalent bifunctional organocatalysis were studied. The results suggest that the bifunctional thioureas can have synthetic limitations in multicomponent domino or autotandem catalysis. Nevertheless, we provided a means to exploit this behavior and used the configuration of the chiral catalyst as a control element in organo-sequential reactions.