A New Dioxazolone for the Synthesis of 1, 2‐Aminoalcohols via Iridium(III)‐Catalyzed C(sp3)−H Amidation. (8th September 2021)

• Record Type: Journal Article
• Authors: Antien, Kevin; Geraci, Andrea; Parmentier, Michael; Baudoin, Olivier
• Is Part Of: Angewandte Chemie. Volume 133:Number 42(2021)
• Page Start: 23130
• Page End: 23137
• Publication Date: 2021-09-08
• Subjects: 1, 2-amino alcohol -- amidation -- C−H activation -- dioxazolone -- iridium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202110019
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Vicinal aminoalcohols are widespread structural motifs in bioactive molecules. We report the development of a new dioxazolone reagent containing a p‐nitrophenyldifluoromethyl group, which 1. displays a good safety profile; 2. shows a remarkably high reactivity in the oxime‐directed iridium(III)‐catalyzed amidation of unactivated C(sp 3 )−H bonds; 3. leads to amide products which can be hydrolyzed under mild conditions. The amidation reaction is mild, general and compatible with both primary C−H bonds of tertiary and secondary alcohols, as well as secondary C−H bonds of cyclic secondary alcohols. This method provides an easy access to free 1, 2‐aminoalcohols after efficient and mild cleavage of the oxime directing group and activated amide. Abstract : A safe and bench‐stable dioxazolone reagent was developed for the oxime‐directed iridium(III)‐catalyzed amidation of unactivated C(sp 3 )−H bonds in tertiary and secondary alcohol‐based substrates. The amidation reaction is mild, general and compatible with both primary and secondary C−H bonds.