American Chemical Society
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Unforeseen 1,2-Aryl Shift in Tetraaryl­pyrrolo­[3,2‑b]­pyrroles Triggered by Oxidative Aromatic Coupling

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journal contribution
posted on 2018-03-07, 14:17 authored by Maciej Krzeszewski, Keisuke Sahara, Yevgen M. Poronik, Takashi Kubo, Daniel T. Gryko
Tetraarylpyrrolo­[3,2-b]­pyrroles (TAPPs) possessing [1,1′-biphenyl]-2-yl substituents attached to the pyrrolic nitrogen atoms undergo selective double dehydrogenative cyclization accompanied by twofold 1,2-aryl migration under oxidative aromatic coupling conditions. The structure of the product of the rearrangement has been unambiguously confirmed by X-ray crystallography, and the reaction pathway is supported by density functional theory (DFT) calculations. Six-membered ring formation (requiring rearrangement of aryl substituents around the core) is energetically preferred over seven-membered ring closure, and a 1,2-aryl shift occurs via arenium cation intermediate.