Synthesis of Nanographenes, Starphenes, and StericallyCongested Polyarenes by Aryne Cyclotrimerization

ConspectusIn recent years, synthetic transformations based on aryne chemistry have become particularly popular, mostly due to the spread of methods to generate these highly reactive intermediates in a controlled manner under mild reaction conditions. In fact, aryne cycloadditions such as the Diels–Alder reaction are nowadays widely used for the efficient preparation of polycyclic aromatic compounds.In 1998, our group discovered that arynes can undergo transition metal-catalyzed reactions, a finding that opened new perspectives in aryne chemistry. In particular, Pd-catalyzed [2 + 2 + 2] cycloaddition of arynes allowed the straightforward synthesis of triphenylene derivatives such as starphenes or cloverphenes. We found that this reaction is compatible with different substituents and sterically demanding arynes as starting materials. This transformation is especially useful to increase the molecular complexity in one single step, transforming molecules formed by n cycles in structures with 3n + 1 cycles. In...