Organic Chemistry

Localized Antiaromaticity Hot-spot Drives Reductive Dehydrogenative Cyclizations in Bis- and Mono-Helicenes

Authors

Abstract

We describe reductive dehydrogenative cyclizations that form hepta-, nona- and decacyclic anionic graphene subunits from mono- and bis-helicenes with an embedded five-membered ring. The reaction of bis-helicenes can either proceed to the full double annulation or be interrupted by addition of molecular oxygen at an intermediate stage. The regioselectivity of the interrupted cyclization cascade for bis-helicenes confirms that relief of antiaromaticity is a dominant force for these facile ring closures. Computational analysis reveals the unique role of the preexisting negatively charged cyclopentadienyl moiety in directing the 2nd negative charge at a specific remote location and, thus, creating a localized antiaromatic region. This region is the hot-spot that promotes the initial cyclization. Computational studies, including MO analysis, molecular electrostatic potential maps, and NICS(1.7)ZZ calculations evaluate the interplay of the various effects including charge delocalization, helicene strain release, and antiaromaticity. The role of antiaromaticity relief is further supported by efficient reductive closure of the less strained mono-helicenes where the relief of antiaromaticity promotes the cyclization even when the strain is substantially reduced. The latter finding significantly expands the scope of this reductive alternative to the Scholl ring closure.

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Supplementary material

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Localized Antiaromaticity Hot-spot Drives Reductive Dehydrogenative Cyclizations in Bis- and Mono-Helicenes
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