Ligand-Controlled Diastereodivergency in Propargylic Alkylation of Vinylogous Aza-Enamines: Construction of 1,3-Stereocenters.

The first diastereodivergent propargylic alkylation reaction is developed. This Cu(I)-catalyzed formal decarboxylative [4+2] cycloaddition between ethynyl benzoxazinanone and vinylogous aza-enamine delivers each diastereomer of tetrahydroquinoline derivatives, bearing 1,3-stereocenters, using either i -Pr-Pybox or BINAP as the ligand under otherwise identical reaction conditions. This is the first application of vinylogous aza-enamines in a transition metal-catalyzed transformation and the first example of the creation of 1,3-stereocenters in a propargylic substitution reaction.