Copper‐Catalyzed Radical Difluoromethylation‐Peroxidation of Alkenes: Synthesis of β‐Difluoromethyl Peroxides

Abstract

A convenient and efficient copper‐catalyzed three‐component difluoromethylation‐peroxidation of alkenes with commercially‐available sodium difluoromethanesulfinate and tert‐butyl hydroperoxide has been developed. This protocol enables the synthesis of a variety of β‐difluoromethyl peroxides under mild conditions. Versatile synthetic transformations of the difluoromethyl peroxides have also been explored.

Synthesis of α/β-Aromatic Peroxy Thiols Mediated by Iodine Source

“…Under the influence of heat, transition metal catalysts, or radiation, the relatively weak O–O bond is cleaved, allowing further synthesis of alcohols, aldehydes, ketones, and other substances. − The bifunctional groups of olefins can rapidly form C–S bonds to synthesize alkyl/arylthiocompounds. − The synthesis methods of peroxides are very diverse, and the bifunctionalization of olefins is often used to synthesize peroxides; some cheap metals are often used as catalysts for reactions. For example, copper can be used as a reaction catalyst to synthesize the target product of peroxides in the strategy using olefins, tert -butyl hydroperoxide (TBHP), and nucleophilic reagents as reactants. ,− Fe is also one of the commonly used catalysts for the synthesis of peroxides. Loh’s group investigated the bifunctionalization of olefins and using Fe as a catalyst.…”

“…In 2019, Yang reported the completion of the bifunctional reaction of diarylphosphonic oxide and peroxide with styrene. Using low-cost Co as a catalyst, the researchers succeeded in providing various phosphonic peroxide products in one pot under mild conditions (Scheme , eq 2) . In 2022, Li developed a convenient and effective copper-catalyzed three-component difluoro methylation peroxide reaction of olefins using sodium difluoromethanesulfonate and tert -butyl hydroperoxide (Scheme , eq 3).…”

“…Using low-cost Co as a catalyst, the researchers succeeded in providing various phosphonic peroxide products in one pot under mild conditions (Scheme 1, eq 2). 22 In 2022, Li 31 developed a convenient and effective copper-catalyzed three-component difluoro methylation peroxide reaction of olefins using sodium difluoromethanesulfonate and tert-butyl hydroperoxide (Scheme 1, eq 3). In 2018, Wang 32 reported the atom-saving, efficient, and environmentally friendly iodine peroxidation of olefins with TBHP and iodine/iodine (Scheme 1, eq 4).…”

Cobalt-catalyzed esterification-peroxidation of α-diazoesters: access to α-acyloxy esters

“…12 In addition, the bifunctional reaction of alkenes has been shown to be an elegant strategy for introducing peroxy groups into the target molecules. 13 Despite significant progress in peroxidation, the development of new synthetic methodologies for the construction of peroxides with structural diversity is still one of the most promising areas in synthetic chemistry.…”