Alkynes as Linchpins for the Additive Annulation of Biphenyls: Convergent Construction of Functionalized Fused Helicenes

• Published in: Angewandte Chemie International Edition Vol. 55; no. 39; pp. 12054 - 12058
• Main Authors: Mohamed, Rana K., Mondal, Sayantan, Guerrera, Joseph V., Eaton, Teresa M., Albrecht-Schmitt, Thomas E., Shatruk, Michael, Alabugin, Igor V.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 19.09.2016; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkynes; Aromatic compounds; Chemical reactions; Chemistry; Chemistry, Multidisciplinary; Computer applications; helicenes; Photochemicals; photocyclodehydroiodination; Physical Sciences; Science & Technology; ACETYLENES; alkynes; PHOTOCHEMICAL-SYNTHESIS; photocyclodehydroiodination; EQUIVALENTS; ENYNE CYCLIZATIONS; RADICAL CASCADES; PHENANTHRENES; helicenes; COUPLING REACTION; TRIPHENYLENE; PHOTOCYCLIZATION; CARBOHELICENES
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201606330

A new approach to fused helicenes is reported, where varied substituents are readily incorporated in the extended aromatic frame. From the alkynyl precursor, the final helical compounds are obtained under mild conditions in a two‐step process, in which the final C−C bond is formed via a photochemical cyclization/ dehydroiodination sequence. The distortion of the π‐system from planarity leads to unusual packing in the solid state. Computational analysis reveals that substituent incorporation perturbs geometries and electronic structures of these nonplanar aromatics. A new approach to fused helicenes is reported, in which varied substituents are readily incorporated in the extended aromatic frame. From an alkynyl precursor, the final helical compounds are obtained in a two‐step process, in which the final C−C bond is photochemically forged by coupling cyclization and dehydroiodination. The distortion of the π‐system from planarity leads to unusual packing in the solid state.