Pd-Catalyzed C–O Bond Formation Enabling the Synthesis of Congested N,N,O-Trisubstituted Hydroxylamines

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A Pd-catalyzed C–O cross-coupling of O -acyl hydroxylamines and tertiary or secondary alkyl electrophiles was reported without the cleavage of the rather fragile N–O bond. The described strategy provides direct access to congested N, N, O -trisubstituted hydroxylamines bearing an α-quaternary carbon center under mild conditions in high yields and features exclusively chemoselective C–O bond formation, a broad substrate scope, and excellent functional group tolerance. The synthetic potential of the cross-coupling was established via pharmaceuticals derivatizations and a series of postcatalytic modifications.