A New Dioxazolone for the Synthesis of 1,2‐Aminoalcohols via Iridium(III)‐Catalyzed C(sp³)−H Amidation

Abstract

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.

Divergent Synthesis, Antiproliferative and Antimicrobial Studies of 1,3‐Aminoalcohol and 3‐Amino‐1,2‐Diol Based Diaminopyrimidines

“…In recent decades, considerable attention has been paid to 1,2‐aminoalcohols, [1–5] 1,3‐aminoalcohols, [6–8] and 3‐amino‐1,2‐diols, [9–14] with the latter combining the chemical properties of 1,2‐ and 1,3‐aminoalcohols. These compounds play a crucial role in numerous branches of human life sciences.…”

Electricity-driven redox-neutral C(sp3)–H amidation withN-alkoxyamide as an amidating reagent

“…In this field, two main types of transformations, C–H activation 2–4 and nitrene insertion, 5–9 have been developed with transition-metal catalysts and activated amidating reagents (Scheme 1). For instance, dioxazolones were employed as an effective amide source in transition metal (Rh, Co, and Ir)-catalyzed sp 3 C–H activation by Li, 2 Seayad, 3 and Baudoin 4 (Scheme 1a). Nitrene insertion was demonstrated as another important strategy for direct C(sp 3 )–H amidation with various catalysts (Scheme 1b).…”

“…Intermolecular C(sp 3 )-H amidation has emerged as an appealing approach for accessing diversely functionalized amides. In this field, two main types of transformations, C-H activation [2][3][4] and nitrene insertion, [5][6][7][8][9] have been developed with transition-metal catalysts and activated amidating reagents (Scheme 1). For instance, dioxazolones were employed as an effective amide source in transition metal (Rh, Co, and Ir)-catalyzed sp 3 C-H activation by Li, 2 Seayad, 3 and Baudoin 4 (Scheme 1a).…”

Rhodium-Catalyzed Ring Expansion of Azetidines via Domino Conjugate Addition/N-Directed α-C(sp3)–H Activation

“…Given the specific structure of the intermediate after the conjugate addition step by calculation, it could be found that the distance between the rhodium atom and methylene C–H is quite close due to the N–Rh coordination, which meets the requirement for C–H activation (Scheme B) . To our delight, it would be a novel N-directed α-C­(sp 3 )–H activation as the N atom usually directs β- or γ-C­(sp 3 )–H activation with transition metal catalysts. ,, The valuable product 2aa , containing the 4-phenyl-4,5-dihydro­pyrrole-3-carboxylate unit, was isolated and identified from the quite mixed products along with similar enamine product 3a , conjugate addition products 4aa and 5a (Scheme C), and others. Since 2-pyrroline and 3,4-disubstituted pyrrolidine are the core structure of many pharmacologically active molecules (Scheme D), it could be a useful synthetic strategy considering the convenient availability of 2-(azetidin-3-ylidene) acetates and aryl boronic acids (Scheme E).…”