Asymmetric synthesis using TBOxM catalyst

ORGN 56

Hisashi Yamamoto, yamamoto@uchicago.edu, Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637
A new class of chiral ligand, tethered bis(8-quinolinol) (TBOxH) is developed. Its chromium complex, TBOxCrCl, (3 mol%) effectively catalyzes the pinacol coupling reaction of aromatic aldehydes at room temperature with high yield (up to 94%), high diastereoselectivity (up to dl : meso = 98 : 2), and high enantioselectivity (up to 98%). The scope of the present method turns out not to be limited to aromatic aldehyde derivatives, as cyclohexanecarboxaldehyde undergoes pinacolization as well (44% yield, dl : meso = 93 : 7, 84% ee). The method provides an efficient access to enantioenriched 1,2-diols. The utility of the new chiral ligand, tethered bis(8-quinolinol) (TBOxH) is further explored. Its chromium complex, TBOxCr(III)Cl, effectively catalyzes the Nozaki-Hiyama allylation reactions of various aldehydes at room temperature with high yield (up to 95%), and high enantioselectivity (up to 99% ee). The scope of the present method is shown to be wide and this method represents an efficient access to chiral homoallylic alcohols.