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Use of the Wilkinson Catalyst for the ortho ‐CH Heteroarylation of Aromatic Amines: Facile Access to Highly Extended π‐Conjugated Heteroacenes for Organic Semiconductors
Author(s) -
Huang Yumin,
Wu Di,
Huang Jingsheng,
Guo Qiang,
Li Juan,
You Jingsong
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201406445
Subject(s) - conjugated system , catalysis , organic semiconductor , chemistry , semiconductor , combinatorial chemistry , photochemistry , materials science , organic chemistry , optoelectronics , polymer
An unprecedented catalytic system composed of the Wilkinson catalyst [Rh(PPh 3 ) 3 Cl] and CF 3 COOH enabled the highly regioselective cross‐coupling of aromatic amines with a variety of heteroarenes through dual CH 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 CH/CH coupling reactions. The current innovative catalyst system is much less expensive than [RhCp*Cl 2 ] 2 /AgSbF 6 and could open the door for the application of this approach to other types of CH activation processes.