Chemodivergent Asymmetric Synthesis via Catalytically Formed Chiral Auxiliary

In summary, the development of the catalytically formed chiral auxiliary concept is described. In this approach, an oxazolidine auxiliary is installed via enantioselective Pd catalysis from readily available starting materials in an enantioselective tethered carboetherification of propargylic amines. Then the formed auxiliary enables diastereoselective functionalization of the formed tetra-substituted olefin moiety. This strategy enables asymmetric hydrogenation, cyclopropanation and epoxidation of C=C bond in highly challenging substrates using simple and robust reaction conditions. Consequently, multiple chemically distinct enantioenriched products - 1,2-aminoalcohols, aminomethyl cyclopropanols and hydroxyketones are obtained by effectively the same chiral catalyst. In the future, the treatment of enantioselectivity and reactivity in separate steps will offer new opportunities in the design of new enantioselective transformations.