Symmetric,Unsymmetrical, and Asymmetric [7]‐, [10]‐, and [13]Helicenes

Fully aromatic helicenes with more than one pitch‐length are illustrious synthetic targets with potential applications in advanced optical devices and nano‐electronics. The task of extending the length of fully conjugated helicenes past one pitch length is challenging. Now, the synthesis of a series of azaoxa7]‐, 10]‐, and 13]helicenes is described. The synthesis is based on iterative oxidative furan formation between 3,6‐dihydroxycarbazoles and/or 2‐naphthols. The flexibility of the presented method allows the convenient and scalable synthesis of symmetric, unsymmetrical, and asymmetric homo‐chiral structures. The 13]helicenes can be synthetically functionalized both at the termini and the periphery. The full range of helicenes were characterized using NMR and optical spectroscopy (UV/Vis, fluorescence, and CD) along with single‐crystal X‐ray crystallography. The enantiomers of the 13]helicenes are the longest optically pure helicenes isolated to date.