First use of axially chiral thioamides for the stereocontrol of C-C bond formation.

Several N-aryl-substituted thioamides with an axis of chirality along the N-C(aryl) bond were prepared in good to excellent yields. NMR spectra revealed preferences for the E rotamer (along the N-C(=S) bond). X-ray crystallographic analysis showed that the planes of the aryl and thioamide groups were almost perpendicular (79 degrees).