Highly Regioselective Domino Benzannulation Reaction of Buta‐1,3‐diynes To Construct Irregular Nanographenes

The properties of nanographenes can be tuned by changing their shapes, therefore the development of new methods suitable for the synthesis of various nanographenes is highly desirable. Described herein is an intramolecular InCl3/AgNTf2‐catalyzed regioselective domino benzannulation reaction of buta‐1,3‐diynes to build irregular nanographenes. Different nanographene compounds were easily obtained in moderate to high yields through careful design of the precursor compounds. This new domino reaction was successfully applied to a fourfold alkyne benzannulation of dimethoxy‐1,1′‐binaphthalene derivatives to arrive at novel chiral butterfly ligand precursors. The regioselectivity of the benzannulation reaction was unambiguously confirmed by X‐ray crystallography. Moreover, this new method enables us to synthesize different nanographene isomers and study their optical properties as a function of shape. Butterfly effect: A series of irregular nanographenes were synthesized by a highly regioselective InCl3/AgNTf2‐catalyzed domino benzannulation of conjugated diynes. A novel chiral butterfly ligand precursor was successfully obtained through this strategy after a fourfold alkyne benzannulation.