Heterocyclic Suzuki–Miyaura coupling reaction of metalla-aromatics and mechanistic analysis of site selectivity. Issue 5 (12th January 2023)

• Record Type: Journal Article
• Authors: Lin, Zuzhang; Cai, Yapeng; Zhang, Yaowei; Zhang, Hong; Xia, Haiping
• Is Part Of: Chemical science. Volume 14:Issue 5(2023)
• Page Start: 1227
• Page End: 1233
• Publication Date: 2023-01-12
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc05455h
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : We describe unique polyhalogenated heteroarene candidates for site-selective cross-coupling, which shows high catalytic performances in the functionalization of polycyclic metalla-aromatics with excellent photophysical properties. Abstract : Pd-catalyzed Suzuki–Miyaura cross-coupling is one of the most straightforward and versatile methods for the construction of functionalized arenes and heteroarenes but site-selective cross-coupling of polyhalogenated (hetero)arenes containing identical halogen substituents remains a challenging problem. Herein, we report a new candidate for heterocyclic Suzuki–Miyaura coupling reaction. This candidate has been applied in organometallic systems by combining classical aryl boronic acid reagents with non-classical heteroarenes. Experimental and computational studies of the mechanism of the reactions were performed, with an emphasis on the identity of the reactive species in the oxidative addition step and the nature of the precise site selectivity. The influence of both the aromaticity of the metalla-aromatic substrates and the steric and electronic properties of the halogenated sites are studied in detail.