Atroposelective Synthesis of N‐Arylated Quinoids by Organocatalytic Tandem N‐Arylation/Oxidation

Diarylamines and related scaffolds are ubiquitous atropisomeric chemotypes in biologically active natural products. However, the catalytic asymmetric synthesis of these axially chiral compounds remains largely unexplored. Herein, we report that a BINOL‐derived chiral phosphoric acid (CPA) successfully catalyzed the atroposelective coupling of quinone esters and anilines through direct C−N bond formation to afford N‐aryl quinone atropisomers with an unprecedented intramolecular N−H−O hydrogen bond within a six‐membered ring in good yields and enantioselectivities with the quinone ester as both the electrophile and the oxidant. A gram‐scale experiment demonstrated the utility of this synthetic protocol. Moreover, this methodology provides a platform for the synthesis of structurally diverse secondary amine atropisomers by nucleophilic addition. A chiral‐phosphoric‐acid‐catalyzed process was developed for the asymmetric synthesis of N‐aryl quinoid atropisomers through direct C−N bond formation. In this way, a broad range of functionalized N‐aryl quinone atropisomers containing an unprecedented intramolecular N−H−O hydrogen bond within a six‐membered ring were constructed in high yields with excellent enantioselectivity.