Palladium-catalyzed multi components oxy-aminofluorination and aminofluorination of gem-difluoroalkenes

Stereoselective hydrodefluorination of CF3-substituted alkenes and gem-difluoroalkenes by H−

“…13 By subjecting 3a to oxidative aminofluorination with N -fluorobenzenesulfonyl imide (NFSI), we obtained the α-difluoroamine product 9 in 62% yield. 14 Additionally, the commercially available Helicid was readily converted into the monofluoroalkene analogue 11 (Scheme 5B).…”

Synthesis of Sterically Hindered Dialkyl Ethers via Palladium-Catalyzed Fluoro-alkoxylation of gem-Difluoroalkenes

“…Following our continuous interest in the synthesis of high-value organofluoro-compounds, herein, we report the palladium-catalyzed fluoroalkoxylation of gem -difluoroalkenes with alcohol donors to give various α-CF 3 ethers, in which an array of sterically challenging dialkyl ethers could be accessed. We suggested that the ethers were formed through the reductive elimination of the C–O bond from the Pd (IV) intermediate after alcohol coordination. , …”

“…This system was further applied to the synthesis of ethers through C(sp 3 )−O cleavage components. 11 Despite these advances, the transition-metal-catalyzed oxidized fluorination of gem-difluoroalkenes using aliphatic alcohols as nucleophilic donors, especially the application of sterically hindered tertsubstituted alkyl alcohols, still needs to be explored. Following our continuous interest in the synthesis of highvalue organofluoro-compounds, 13 herein, we report the palladium-catalyzed fluoroalkoxylation of gem-difluoroalkenes with alcohol donors to give various α-CF 3 ethers, in which an array of sterically challenging dialkyl ethers could be accessed.…”

“…We suggested that the ethers were formed through the reductive elimination of the C−O bond from the Pd (IV) intermediate after alcohol coordination. 11,14 We initiated our studies by investigating the reaction conditions of gem-difluoroalkene 1a, NFSI, and tert-butanol 2a in the presence of Pd(OAc) 2 catalyst (Table 1; for more details, see Table S1 in Supporting Information). The ligand structure was important to give sterically hindered ether 3a.…”

“…The aminofluorination product 3a′ was the only byproduct under these conditions (entries 10−17). 11 The addition of Mg(OTf) 2 was beneficial for the generation of 3a and decreased the yield of byproduct 3a′ (entries 19−20). Furthermore, the product 3a can be obtained in 71% yield with excellent regio-and chemo-selectivity with t BuOH/DCE as a solvent (entry 21).…”