Metal-Free Synthesis of Benzothiophenes by Twofold C−H Functionalization: Direct Access to Materials-Oriented Heteroaromatics

Yan, Jiajie, Pulis, Alexander P., Perry, Gregory J.P. and Procter, David J. (2019) Metal-Free Synthesis of Benzothiophenes by Twofold C−H Functionalization: Direct Access to Materials-Oriented Heteroaromatics. Angewandte Chemie - International Edition, 58 (44), 15675-15679. (doi:10.1002/anie.201908319).

Record type: Article

Abstract

Due to their ubiquity in nature and frequent use in organic electronic materials, benzothiophenes are highly sought after. Here we set out an unprecedented procedure for the formation of benzothiophenes by the twofold vicinal C−H functionalization of arenes that does not require metal catalysis. This one-pot annulation proceeds through an interrupted Pummerer reaction/[3,3]-sigmatropic rearrangement/cyclization sequence to deliver various benzothiophene products. The procedure is particularly effective for the rapid synthesis of benzothiophenes from non-prefunctionalized polyaromatic hydrocarbons (PAHs).

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Published date: 28 October 2019

Additional Information: Funding Information: We thank the EPSRC (Established Career Fellowship to D.J.P.; EP/M005062/1), the University of Manchester (Lectureships to A.P.P. and G.J.P.P), the Swedish Chemical Society (Stiftelsen Bengt Lundqvists Minne Postdoc Fellowship to J.Y.), the Manchester X-ray Crystallography Service, and Prof. Kenichiro Itami, Assoc. Prof. Kei Murakami, Assoc. Prof. Hideto Ito, Wataru Matsuoka, Shu Jan Yip, Kou Kawahara and all the Itami group for discussions and for the gift of corannulene. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords: annulation, benzothiophene, Pummerer reaction, sulfur, π-extension