Gold‐Catalyzed Direct C(sp3)−H Acetoxylation of Saturated Hydrocarbons. Issue 19 (23rd August 2021)

• Record Type: Journal Article
• Authors: Jo, Tae Geun; Klein, Johannes E. M. N.
• Is Part Of: ChemCatChem. Volume 13:Issue 19(2021)
• Page Start: 4087
• Page End: 4091
• Publication Date: 2021-08-23
• Subjects: Acetoxylation -- Gold Catalysis -- Hydride Transfer -- Hydrocarbon Oxidation; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.202100804
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: In this communication we report our studies towards the development of a gold‐catalyzed direct acetoxylation of C(sp 3 )−H bonds. We achieve this through the use of the hypervalent iodine reagent PhI(OAc)2 in combination with a simple gold salt (HAuBr4 ) as the catalyst. Through a comparison of the reactivities of cyclooctane and adamantane we judge the reaction to proceed via hydride transfer. This is further substantiated through computational studies of the relative energies for the anions, radicals and cations derived from C−H bond cleavage of cyclooctane and adamantane relevant to the C−H cleaving step. Abstract : Gold catalysis : A protocol for the direct acetoxylation of C(sp 3 )−H bonds of saturated hydrocarbons using simple gold salts (e. g. HAuBr4 ) is reported. PhI(OAc)2 serves as the oxidant and this transformation is proposed to proceed via hydride transfer as the key step.