- New sulfuryl fluoride-derived alkylating reagents for the 1,1-dihydrofluoroalkylation of thiols
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Herein, we report a new method for the one-pot synthesis of 1,1-dihydrofluoroalkyl sulfides by bubbling sulfuryl fluoride (SO2F2) through a solution of the corresponding alcohol and thiol. The reaction proceeds through a new class of bis(1,1-dihydrofluoroalkyl) sulfate reagents, to afford the desired 1,1-dihydrofluoroalkyl sulfides in 55-90% isolated yields. The bis(1,1-dihydrofluoroalkyl) sulfates are highly chemoselective for thiol alkylation, and are unreactive with competing, unprotected nucleophiles, including amines, alcohols, and carboxylic acids.
- Foth, Paul J.,Gu, Frances,Bolduc, Trevor G.,Kanani, Sahil S.,Sammis, Glenn M.
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p. 10331 - 10335
(2019/11/20)
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- Copper-Catalyzed Insertion into Heteroatom-Hydrogen Bonds with Trifluorodiazoalkanes
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Copper-catalyzed Si-H, B-H, P-H, S-H, and N-H insertion reactions of 2,2,2-trifluoro-1-diazoethane and 1-aryl 2,2,2-trifluorodiazoethanes generated a large number of new fluorine-containing chemical entities for medicinal chemists. With selected Si-H and
- Hyde, Stephen,Veliks, Janis,Liégault, Beno?t,Grassi, David,Taillefer, Marc,Gouverneur, Véronique
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supporting information
p. 3785 - 3789
(2016/03/23)
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- Synthesis of alkyl perfluoroalkanedithiocarboxylates and some aspects of their reactivity in cycloaddition reactions
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A new method for the synthesis of the title compounds is proposed.The starting fluorinated compounds are commercially available trifluoroethanol and higher homologues, which were transformed in three steps into (2,2-dichloroperfluoroalkyl) alkylsulfides.The last step consisted in a substitution of chlorine by sulfur by treatment with zinc sulfide.The source of zinc sulfide is crucial and the possible role of catalytic impurities was investigated.These dithioesters are excellent dienophiles.Some cycloaddition reactions with 2,3-dimethylbuta-1,3-diene and 1-(trimethylsilyloxy)buta-1,3-diene are reported. - Keywords: perfluorinated dithioester; polyfluorinated sulfide; cycloaddition; tetrahydrothiopyran
- Portella, Charles,Shermolovich, Yuri G.,Tschenn, Olivier
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p. 697 - 702
(2007/10/03)
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- Chemoselective reaction of a sulfonate ester with methoxide ions in preference to benzyl mercaptide anions
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Trifluoroethyl benzyl sulfide was prepared (in 2-propanol) and subsequently chlorinated as a further test of substituent electronegativity based regiochemical predictions.The initial attempt to prepare that sulfide by reaction of 2,2,2-trifluoroethyl methanesulfonate and benzyl mercaptide anions (in methanol) furnished benzyl methyl sulfide.Mechanistic possibilities are discussed in detail and some synthetic consequences of this novel reaction are presented.
- Langler, Richard Francis,Morrison, Nancy Ann
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p. 2385 - 2389
(2007/10/02)
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- SYNTHESIS OF THREE PARTIALLY FLUORINATED ALKANESULFONIC ACIDS AS POTENTIAL FUEL-CELL ELECTROLYTES.
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The simple and effective syntheses of CH//2FCH//2SO//3H, CF//3CH//2SO//3H, AND CHF//2CF//2CH//2SO//3H have been achieved with 18. 8%, 34. 1%, and 33. 7% overall yields. The low molecuar weight partially fluorinated alkanesulfonic acids containing alpha -methylene groups can be prepared from the p-toluenesulfonates of the corresponding alcohols, via a reaction with benzyl mercaptan, followed by an oxidative chlorination of the resulting sulfides, with subsequent hydrolysis of the sulfonyl chloride. The reaction of partially fluorinated alkyl halides with sodium sulfite (Strecker's method) proved to be inefficient (very low yields) and unreliable. The sulfonate salts formed are difficult to recover and purify.
- Bunyagidj,Piotrowska,Aldridge
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p. 344 - 346
(2007/10/02)
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