Synthetic Applications of Oxidative Aromatic Coupling—From Biphenols to Nanographenes

• Published in: Angewandte Chemie International Edition 2020-02, Vol.59 (8), p.2998-3027
• Main Authors: Grzybowski, Marek, Sadowski, Bartłomiej, Butenschön, Holger, Gryko, Daniel T.
• Format: Article
• Language: English
• Subjects: Aromatic compounds; biaryls; Chemical synthesis; Coupling (molecular); Dehydrogenation; Lewis acids; nanographenes; Natural products; Organic chemistry; oxidative coupling; Reagents; Review; Reviews; Scholl reaction
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201904934

Oxidative aromatic coupling occupies a fundamental place in the modern chemistry of aromatic compounds. It is a method of choice for the assembly of large and bewildering architectures. Considerable effort was also devoted to applications of the Scholl reaction for the synthesis of chiral biphenols and natural products. The ability to form biaryl linkages without any prefunctionalization provides an efficient pathway to many complex structures. Although the chemistry of this process is only now becoming fully understood, this reaction continues to both fascinate and challenge researchers. This is especially true for heterocoupling, that is, oxidative aromatic coupling with the chemoselective formation of a C−C bond between two different arenes. Analysis of the progress achieved in this field since 2013 reveals that many groups have contributed by pushing the boundary of structural possibilities, expanding into surface‐assisted (cyclo)dehydrogenation, and developing new reagents. Coupling up: The dehydrogenative coupling of arenes is an ultimate example of C−H activation. This Review highlights the most exciting examples of the Scholl reaction, ranging from the synthesis of biphenols through natural products to nanographenes and on‐surface dehydrogenation reported since 2013.