An enantioselective Cu(I)-catalyzed coupling of N-carboxyindoles with various 2-naphthols and phenols for the synthesis of axially chiral arylindoles has been developed. Our mechanistic studies, bolstered by experimental evidence and DFT calculations, reveal a novel closed-shell mechanism involving outer-sphere attack of N-carboxyindoles on the Cu-bound naphthols. This mechanism allows for unprecedented diversity of 2-naphthols and phenols in C-H arylation. Enantiocontrol is achieved through center-to-axis chirality transfer via a key dearomatized naphthol intermediate, which prevents undesired epimerization of the C-C axis.
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