Vicinal aminoalcohols are widespread structural motifs in bioactive molecules.W er eport the development of anew dioxazolone reagent containing ap-nitrophenyldifluoromethyl group,which1.displays agood safety profile;2.shows ar emarkably high reactivity in the oxime-directed iridium-(III)-catalyzed amidation of unactivated C(sp 3 ) À Hb onds;3 . leads to amide products whichc an be hydrolyzed under mild conditions.T he amidation reaction is mild, general and compatible with both primary CÀHb onds of tertiary and secondary alcohols,aswell as secondary CÀHbonds of cyclic secondary alcohols.T his method provides an easy access to free 1,2-aminoalcohols after efficient and mild cleavage of the oxime directing group and activated amide.

Vicinal aminoalcohols are widespread structural motifs in bioactive molecules.W er eport the development of anew dioxazolone reagent containing ap-nitrophenyldifluoromethyl group,which1.displays agood safety profile;2.shows ar emarkably high reactivity in the oxime-directed iridium-(III)-catalyzed amidation of unactivated C(sp 3 ) À Hb onds;3 . leads to amide products whichc an be hydrolyzed under mild conditions.T he amidation reaction is mild, general and compatible with both primary CÀHb onds of tertiary and secondary alcohols,aswell as secondary CÀHbonds of cyclic secondary alcohols.T his method provides an easy access to free 1,2-aminoalcohols after efficient and mild cleavage of the oxime directing group and activated amide.

Chiral 1,2‐diamines are privileged scaffolds among bioactive natural products, active pharmaceutical ingredients, ligands for transition‐metal‐based asymmetric catalysis and organocatalysts. Despite this interest, the construction of chiral 1,2‐diamine motifs still remains a challenge. To address this, an iridium(III)‐catalyzed intermolecular C(sp3)–H amidation reaction was developed. This method relies on the design of a new, cheap and cleavable exo‐protecting/directing group derived from camphorsulfonic acid, which is directly installed from easily accessible precursors, and furnishes scalemic free 1,2‐diamines upon cleavage of both nitrogen substituents. It was found applicable to both α‐secondary and α‐tertiary‐1,2‐diamines, for which a two‐step protocol involving intermolecular olefin hydroamination and C(sp3)–H amidation was developed. Kinetic and computational studies provided insights into the observed reactivity difference between pairs of diastereoisomeric substrates.

Chiral 1,2‐diamines are privileged scaffolds among bioactive natural products, active pharmaceutical ingredients, ligands for transition‐metal‐based asymmetric catalysis and organocatalysts. Despite this interest, the construction of chiral 1,2‐diamine motifs still remains a challenge. To address this, an iridium(III)‐catalyzed intermolecular C(sp3)–H amidation reaction was developed. This method relies on the design of a new, cheap and cleavable exo‐protecting/directing group derived from camphorsulfonic acid, which is directly installed from easily accessible precursors, and furnishes scalemic free 1,2‐diamines upon cleavage of both nitrogen substituents. It was found applicable to both α‐secondary and α‐tertiary‐1,2‐diamines, for which a two‐step protocol involving intermolecular olefin hydroamination and C(sp3)–H amidation was developed. Kinetic and computational studies provided insights into the observed reactivity difference between pairs of diastereoisomeric substrates.