title: Use of the Wilkinson catalyst for the ortho-C-H heteroarylation of aromatic amines: facile access to highly extended π-conjugated heteroacenes for organic semiconductors.
abstract: An unprecedented catalytic system composed of the Wilkinson catalyst [Rh(PPh3)3Cl] and CF3COOH enabled the highly regioselective cross-coupling of aromatic amines with a variety of heteroarenes through dual C-H bond cleavage. This protocol provided a facile and rapid route from readily available substrates to (2-aminophenyl)heteroaryl compounds, which may be conveniently transformed into highly extended π-conjugated heteroacenes. The experimental studies and calculations showed that thianaphtheno[3,2-b]indoles have large HOMO-LUMO energy gaps and low-lying HOMO levels, and could therefore potentially be high-performance organic semiconductors. Herein we report the first use of a rhodium(I) catalyst for oxidative C-H/C-H coupling reactions. The current innovative catalyst system is much less expensive than [RhCp*Cl2]2/AgSbF6 and could open the door for the application of this approach to other types of C-H activation processes.
authors.affiliation: Key Laboratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
authors.forename: Yumin
authors.initials: Y
authors.lastname: Huang
authors.forename: Di
authors.initials: D
authors.lastname: Wu
authors.forename: Jingsheng
authors.initials: J
authors.lastname: Huang
authors.forename: Qiang
authors.initials: Q
authors.lastname: Guo
authors.forename: Juan
authors.initials: J
authors.lastname: Li
authors.forename: Jingsong
authors.initials: J
authors.lastname: You
mesh_terms: D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D010084:Oxidation-Reduction; D012666:Semiconductors
chemical_list: D000588:Amines
keywords: Wilkinson catalyst; aromatic amines; heteroarylation; organic semiconductors; oxidative cross-coupling