Using the “lactone concept”, differently substituted AB-biaryl fragments (P)-2 (R= Me, t-Bu) of vancomycin have been synthesized atroposelectively. Their otherwise configurational instability was remedied by inclusion of two chlorine atoms in the B ring to give (M)-29. Starting from a still configurationally unstable lactone-bridged precursor, we obtained this biaryl with high atroposelectivity (dr 94: 6) by ring cleavage with dynamic kinetic ...