Described herein is the Ir-catalyzed enantioselective access to chiral spirolactam products via the nitrenoid transfer to aromatic -carbons. The key strategy for precise stereocontrol is to enhance the secondary attractive and repulsive interactions between the chiral catalyst and substrates by the introduction of a traceless -silyl achiral auxiliary, thus effectively differentiating two prochiral faces of arenol-derived 1,4,2-dioxazol-5-one substrates.

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http://dx.doi.org/10.1021/jacs.1c02550DOI Listing

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