Herein, we report a controlled introduction of an amide unit at the ortho-position of an electron-deficient arylamide system without affording any cyclized products using user-friendly dioxazolone as an amidating reagent in the presence of a Rh(III)-catalyst. This is the first report where native primary amide has been utilized as a weakly coordinating group for site-selective C-N bond formation reaction. The developed protocol works under external auxiliary-free conditions with a wide substrate scope.

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http://dx.doi.org/10.1021/acs.joc.4c00116DOI Listing

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