Hornillos, Valentin , CARMONA CARMONA, JOSÉ ALBERTO, Ros, Abel , Iglesias-Siguenza, Javier , Lopez-Serrano, Joaquin , Fernandez, Rosario , Lassaletta, Jose M.
Si
Angew. Chem.-Int. Edit.
Article
Científica
12.257
26/03/2018
000428350100043
A diastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile heterobiaryl ketones is described. The DKR proceeds by zinc-catalyzed hydrosilylation of the carbonyl group, thus leading to secondary alcohols bearing axial and central chirality. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a Lewis acid-base interaction between a nitrogen atom in the heterocycle and the ketone carbonyl group. The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N,N-ligands or appealing axially chiral, bifunctional thiourea organocatalysts.
asymmetric catalysis; axial chirality; dynamic kinetic resolution; hydrosilylation; ligand design