An efficient and straightforward approach for the synthesis of C7 site-selective BINOL derivatives has been achieved via cost-effective Co­(III)-catalyzed C–H cascade alkenylation/intramolecular Friedel–Crafts alkylation of BINOL units and propargyl cycloalkanols. Under the advantage of the pyrazole directing group, the protocol allows the rapid synthesis of various BINOL-tethered spiro­[cyclobutane-1,1′-indenes].

Intramolecular C−H activation/C−O coupling, dearomatization, and [4+2] cycloaddition of BINOL units have been well developed in a one-pot approach with maleimide derivatives as the dienophiles. This tandem catalytic system generates a variety of functionalized bridged polycyclic products in a step-economical manner, which greatly enriches the modification methods and strategies for the BINOL skeletons.

Rhodium(III)‐catalyzed cross‐dehydrogenative coupling involves a highly efficient C−C bond formation from N‐phenyl‐7‐azaindole frameworks, thiophenes. Various novel 7‐azaindole derivatives have been successfully developed with good substrate applicability.