Synthesis and structural characterization. Firstly, chiral benzophenone derivatives RB-X and SB-X were readily obtained via Friedel-Crafts acylation between benzoyl chloride and BINOL moiety with defined axis chirality in presence of AlCl 3 (Scheme 1). Then, the intermolecular McMurry coupling of RB-X or SB-X could directly yield the macrocycles RBT-X and SBT-X with satisfactory yield (Scheme 1a). The chemical identities of these chiral macrocycles were firstly confirmed by H nuclear magnet- ic resonance (NMR) spectroscopy, whereas all proton signals had been unambiguously assigned with the assistance of 1 H-1 H 2D correlation spectroscopy and nuclear Overhauser effect spectroscopy (Figure ). In addition, the matrix-assisted laser ionization time-of-flight (MALDI-TOF) mass spectra for RBT-X and SBT-X also directly indicated the species with desired molar mass, and the experimental isotopic distributions also agreed well with their simulated patterns (Figure -S10).