Challenging Atroposelective C–H Arylation

Abstract

Atropisomeric molecules are privileged scaffolds, not only as ligands for asymmetric synthesis, but also as biologically active products and advanced materials. Although very attractive from a sustainability viewpoint, the direct construction of the stereogenic axis through asymmetric C–H arylation is very challenging and consequently only a few examples have been reported. This short review summarizes these very recent results on the atropo-enantio or diastereo­selective synthesis of atropisomeric (hetero)biaryl molecules; transformations during which the Ar–Ar atropisomeric axis is formed during the C–H activation process. 1 Introduction 2 Atropo-enantioselective Intermolecular Pd-Catalyzed C–H Arylation of Thiophene Derivatives 3 Atropodiastereoselective Intermolecular Pd-Catalyzed C–H Arylation towards Terphenyl Scaffolds Bearing Two Atropisomeric Axes 4 Atropo-enantioselective Intramolecular Pd-Catalyzed C–H Arylation towards Atropisomeric Benzodiazepinones 5 Atropo-enantioselective Intermolecular Pd-Catalyzed C–H Arylation of Heteroarenes 6 Rh-Catalyzed Atropo-enantioselective C–H Arylation of Diazonaphthoquinones 7 Conclusion

Keywords

• atropisomeric axis
• atropisomeric biaryls
• c–h arylation