Abstract
Cationic Ir(I)-complexes modified with homochiral diphosphines promote the α-C-H addition of α-hydroxy ketones to styrenes or alkyl olefins. These processes are predicated on the hydroxyl-directed formation of an Ir-enolate. Inter- and intramolecular processes are feasible, with the latter offering stereocontrolled access to carbocycles bearing two new stereocenters. The intramolecular processes constitute rare examples of alkene-based Conia-ene reactions that are enantio- and diastereoselective.