A diselenide additive enables photocatalytic hydroalkoxylation ofgem-difluoroalkenes

Abstract

A photocatalytic hydroalkoxylation reaction enables the coupling of aliphatic alcohols with gem-difluoroalkenes, expanding the scope of accessible α,α-difluorinated ethers, a desirable substructure for medicinal and agricultural chemists. This reaction exploits...

Metal-Free Cyanation of gem-Difluoroalkenes via Azide-Mediated C–C Double Bond Fragmentation

“…Perhaps more importantly, gem -difluoroalkenes can be easily prepared from commercially available carbonyl compounds via Wittig, Julia-Kocienski, and Horner–Wadsworth–Emmons-type reactions, offering expandable and attractive chemical space for the development of synthetically useful transformations. Thanks to their rich reactivities, a range of elegant strategies have been exploited for the conversion of gem -difluoroalkenes into structurally diverse architectures, including nucleophilic addition, radical-mediated defluorinative functionalization, hydrodefluorination, hydroamination, hydroboration, hydrosilylation, hydroalkoxylation, fluoroarylation, carboxylation, and sulfuration . These studies have predominantly relied on the functionalization of C–C double bonds and the selective transformation of C–F bonds in gem -difluoroalkenes (Scheme a).…”

Photoredox-Catalyzed gem-Difluoromethylenation of Aliphatic Alcohols with 1,1-Difluoroalkenes to Access α,α-Difluoromethylene Ethers

“…The drawbacks of catalyst and product selectivity significantly reduced the practicability of the method. Very recently, Altman and co-workers reported a photocatalytic hydroalkoxylation reaction, which involved generating radical cations via the photooxidation of gem -difluoroalkenes to construct CF 2 ―O bonds …”

Difunctionalization of gem-difluoroalkenes for amination and heteroarylation via metal-free photocatalysis

“…[8][9][10] Recent research on functionalization of gem-difluoroalkenes has mainly focused on the construction of C-X (X = OR, SR, etc.) or C(sp3)-C(sp3) bonds, involving the introduction of some functional groups such as alkyl, [11][12][13] alkoxyl, 14,15 alkylthiol, 16,17 sulfonyl 18 and other groups (Scheme 1a). 9,10,19,20 However, there are only a few reports on the introduction of aromatic groups to gemdifluoroalkenes, and previous reports focused on transitionalmetal catalyzed coupling reactions (Scheme 1a).…”