Rhodium-catalyzed ortho-heteroarylation of phenols: directing group-enabled switching of the electronic bias for heteroaromatic coupling partner. Issue 33 (25th July 2018)

• Record Type: Journal Article
• Authors: Wu, Yimin; Li, Wei; Jiang, Linfeng; Zhang, Luoqiang; Lan, Jingbo; You, Jingsong
• Is Part Of: Chemical science. Volume 9:Issue 33(2018)
• Page Start: 6878
• Page End: 6882
• Publication Date: 2018-07-25
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c8sc02529k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : A highly efficient ortho -heteroarylation of phenols with diverse electron-rich heteroarenes has been developed to forge heteroaryl-2-hydroxyphenyl structural motifs. The removal of the directing group and subsequent intramolecular cyclization make this protocol applicable in the rapid construction of π-conjugated heteroacenes. Abstract : The directed oxidative C–H/C–H cross-coupling reactions between a functionalized arene and a heteroarene typically exhibit an electronic bias for the heteroaromatic coupling partner. Disclosed herein is a conception of directing group enabled-switching of the electronic bias for coupling partner from the electron-deficient to electron-rich heteroarene, demonstrating that the modification of the directing group may match the latent reactivity of heteroarene substrates caused by the distinctly different electronic nature. In this work, we develop a Rh(iii )-catalyzed ortho -heteroarylation of phenols with greatly important electron-rich heteroarenes such as benzothiophene, benzofuran, thiophene, furan and pyrrole via two-fold C–H activation, which presents broad substrate scopes of both phenols and electron-rich heteroarenes and shows the advantage of tolerance of reactive functional groups, especially halogen. This work also provides a new strategy for the construction of π-conjugated furan-fused heteroacenes prevalent in materials science in dramatically simplified procedures, which makes the protocol highly applicable.