Optical resolution of 1,16-dihydroxytetraphenylene by chiral gold(iii) complexation and its applications as chiral ligands in asymmetric catalysis.

We report herein a novel approach involving optical resolution of (±)-1,16-dihydroxytetraphenylene (DHTP) by chiral gold(iii) complexation. This method features several key advantages, i.e. , recyclability of chiral resolution reagents, feasibility of scaling up to gram quantities, and operational simplicity. On the basis of this method, which led to optically pure DHTP, a library of 2,15-diaryl ( S )-DHTPs and several ( S )-DHTP-derived phosphoramidite ligands were synthesized. Finally, the superior performance of a ( S )-DHTP phosphoramidite ligand was demonstrated by efficient iridium-catalyzed asymmetric allylic alkynylation reactions.