Cu(I)-Catalyzed\nAtropselective Heterobiaryl Coupling\nEmploying Umpoled Indoles

An\nenantioselective Cu(I)-catalyzed coupling of N-carboxyindoles\nwith various 2-naphthols and phenols for the synthesis of axially\nchiral arylindoles has been developed. Our mechanistic studies, bolstered\nby experimental evidence and DFT calculations, reveal a novel closed-shell\nmechanism involving outer-sphere attack of N-carboxyindoles on the\nCu-bound naphthols. This mechanism allows for unprecedented diversity\nof 2-naphthols and phenols in C–H arylation. Enantiocontrol\nis achieved through center-to-axis chirality transfer via a key dearomatized\nnaphthol intermediate, which prevents undesired epimerization of the\nC–C axis.