Herein we report the development of deacylative thiolation of diverse methyl ketones. The reaction is redox‐neutral, and heavy‐metal‐free, which provides a new way to introduce thioether groups ...site‐specifically to unactivated aliphatic positions. It also features excellent functional group tolerance and broad substrate scope, thus allowing late‐stage derivatization. The process benefits from efficient condensation between the activation reagent and ketone substrates, which triggers aromatization‐driven C−C fragmentation and rapid radical coupling with thiosulfonates. Experimental and computational mechanistic studies suggest the involvement of a radical chain pathway.
A redox‐neutral, heavy‐metal‐free approach has been developed to realize deacylative thiolation of common ketones, which provides a unique method to introduce thioether groups site‐specifically to unactivated aliphatic positions. Experimental and computational mechanistic studies suggest the involvement of a radical chain pathway.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Trifluoromethylthiolation and trifluoromethylselenolation of 3- or 4-iodo(bromo)-2-pyrones with (bpy)CuSCF3 and (bpy)CuSeCF32 provide a convenient method for the synthesis of ...trifluoromethylthio(seleno)lated 4-alkoxy-, aryloxy-, and benzyloxy-2-pyrones in high yields.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
A method for direct difluoromethylthiolation of Ar−H bonds is introduced. The stable and easy‐to‐handle HCF2SO2Na is reduced with (EtO)2P(O)H in the presence of TMSCl to generate HCF2S+ for the ...regioselective difluoromethylthiolation of aromatic compounds including indoles, pyrroles, and activated benzenes. This method is also applicable for the trifluoromethylthiolation with CF3SO2Na and the perfluoroalkylthiolation with RfSO2Na of arenes and heteroarenes. Reaction mechanisms associated with the metal‐free electrophilic fluoroalkylthiolation reactions are also discussed.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
A silver-mediated cascade trifluoromethylthiolation and cyclization has been developed for the synthesis of 2-(trifluoromethylthio)-indenones. A variety of arylpropynones underwent this radical ...oxidative cyclization with AgSCF3 to afford trifluoromethylthiolated indenones in moderate to excellent yields.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Trifluoromethanesulfonic anhydride has been widely used in synthetic organic chemistry, not only for the conversion of various oxygen‐containing compounds to the triflates, but also for the ...electrophilic activation and further conversion of amides, sulfoxides, and phosphorus oxides. In recent years, the utilization of Tf2O as an activator for nitrogen‐containing heterocycles, nitriles and nitro groups has become a promising tool for the development of new valuable methods with considerable success. In addition, Tf2O has been used as an efficient radical trifluoromethylation and trifluoromethylthiolation reagent due to the contained SO2CF3 fragment, and significant progress has been made in this area. This review summarizes the recent progress in the applications of Tf2O in the above two aspects, and aims to illustrate the role and potential application of this reagent in organic synthesis.
Tf2O has been widely used in synthetic chemistry. This review summarizes the recent progresses of Tf2O as an activator for nitrogen‐containing heterocycles, nitriles, and nitro groups for the development of new reactions, and as an efficient radical trifluoromethylation and trifluoromethylthiolation reagents in organic synthesis.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Trifluoromethylthiolation-peroxidation of unactivated alkenes using readily-available AgSCF3 and tert-butyl hydroperoxide has been realized in the presence of the copper catalyst. The radical ...trifluoromethylthiolation of alkenes triggers a 1,5-HAT and further remote α-CH bond peroxidation to afford a series of distal trifluoromethylthiolated organic peroxides in moderate to good yields with excellent regioselectivity under mild conditions.
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Trifluoromethylthiolation-peroxidation of unactivated alkenes using readily-available AgSCF3 and tert-butyl hydroperoxide has been realized in the presence of the copper catalyst. The radical trifluoromethylthiolation of alkenes triggers a 1,5-HAT and further remote α-CH bond peroxidation to afford a series of distal trifluoromethylthiolated organic peroxides in moderate to good yields with excellent regioselectivity under mild conditions.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Direct dehydroxytrifluoromethylthiolation of enols and electron-deficient phenols with AgSCF3 in the presence of n-Bu4NI and KI is reported, affording a series of vinyl and aryl trifluoromethyl ...sulfides in moderate to excellent yields. This work represents a rare example of direct functionalization of Csp2−OH bonds.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
A catalyst‐ and additive‐free decarbonylative trifluoromethylthiolation of aldehyde feedstocks has been developed. This operationally simple, scalable, and open‐to‐air transformation is driven by the ...selective photoexcitation of electron donor‐acceptor (EDA) complexes, stemming from the association of 1,4‐dihydropyridines (donor) with N‐(trifluoromethylthio)phthalimide (acceptor), to trigger intermolecular single‐electron transfer events under ambient‐ and visible light‐promoted conditions. Extension to other electron acceptors enables the synthesis of thiocyanates and thioesters, as well as the difunctionalization of 1.1.1propellane. The mechanistic intricacies of this photochemical paradigm are elucidated through a combination of experimental efforts and high‐level quantum mechanical calculations dispersion‐corrected (U)DFT, DLPNO‐CCSD(T), and TD‐DFT. This comprehensive study highlights the necessity for EDA complexation for efficient alkyl radical generation. Computation of subsequent ground state pathways reveals that SH2 addition of the alkyl radical to the intermediate radical EDA complex is extremely exergonic and results in a charge transfer event from the dihydropyridine donor to the N‐(trifluoromethylthio)phthalimide acceptor of the EDA complex. Experimental and computational results further suggest that product formation also occurs via SH2 reaction of alkyl radicals with 1,2‐bis(trifluoromethyl)disulfane, generated in‐situ through combination of thiyl radicals.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Abstract
The new millennium has witnessed the rapid development of synthetic organofluorine chemistry all over the world, and chemists in China have made significant contributions in this field. This ...review aims to provide a brief introduction to China's primary innovations from 2000 to early 2017, covering fluorination, fluoroalkylation, fluoromethylthiolation, fluoroolefination and polyfluoroarylation, as well as synthesis with fluorinated building blocks. Recent advances in the chemistry of difluorocarbene and the chemistry of carbon–fluorine bond activation are also discussed. As a conclusion, the review ends with some personal perspectives on the future development of China's synthetic organofluorine chemistry.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
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