Gram-Scale Synthesis of the 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes

A gram-scale synthesis of a series of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n=7-9) has been accomplished as well as the first synthesis of the next higher homologue 1,1,10,10-tetramethyl[10](2,11)teropyrenophane. The scale-up of the original small-scale synthesis required the development of several heavily modified synthetic methods, including a chlorination/Friedel-Crafts alkylation protocol and an iodination/Wurtz coupling protocol, which were performed on 25-30 g and 30-60 g scales, respectively. Two separate sets of conditions for the key teropyrene-forming cyclodehydrogenation reaction at the end of the synthetic pathway were developed, an acid-promoted one for the two less strained congeners and an acid-free method for the two more strained homologues.