- FLP-Catalyzed Monoselective C-F Functionalization in Polyfluorocarbons at Geminal or Distal Sites
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We report frustrated Lewis pair (FLP)-catalyzed monoselective C-F activation in a range of aliphatic polyfluorocarbons with equivalent geminal and distal C-F positions. This methodology can be applied to aromatic-, ether-, thioether-, and alkyl-supported fluoromethyl groups. We expand the range of FLP base partners that work with monoselective C-F activation to include sulfide. The activated products can be subsequently functionalized via SN2 substitutions, photoredox-alkylations, and Suzuki couplings.
- Gupta, Richa,Mandal, Dipendu,Jaiswal, Amit K.,Young, Rowan D.
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p. 1915 - 1920
(2021/04/05)
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- Synthesis of monofluoromethylcyclopropanes from alkenes without using freons: Novel synthesis of chlorofluoromethyl phenyl sulfide and its application in cyclopropanation
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Chlorofluoromethyl phenyl sulfide was prepared from the reaction of chloromethyl phenyl sulfide with Selectfluor. Monofluorocyclopropanation of an alkene was achieved via cyclopropanation using a fluorocarbene derived from the product chlorofluoromethyl phenyl sulfide, followed by oxidation and desulfurization.
- Kirihara, Masayuki,Ogata, Tomomi,Itou, Atsushi,Naito, Sayuri,Kishida, Mari,Yamazaki, Kento,Tabata, Hidetsugu,Takahashi, Hideyo
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p. 1377 - 1379
(2013/11/19)
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- Chemistry of trichlorofluromethane: Synthesis of chlorofluromethyl phenyl sulfone and fluoromethyl phenyl sulfone and some of their reactions
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It was observed that the reaction of CFCl3 with thiophenoxide gave only 10% of the corresponding thioether. On the other hand, these thioethers could be prepared in excellent yield from diaryl disulfides and CFCl3 in the presence of sodium hydroxymethanesulfinate in aqueous DMF at 4 atm pressure of nitrogen. Dechlorination of the thioether (PhSCFCl2) with different reducing agents were studied. Most of the reducing agents eliminated both fluorine and chlorine functionalities or gave the hydrolyzed products. But its sulfone on treatment with Zinc in methanol gave monochlorofluoromethyl and fluoromethyl phenyl sulfone in good yields. Darzens reaction of these compounds was also studied.
- Saikia,Tsuboi
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p. 643 - 647
(2007/10/03)
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- Behaviors of α-Fluorocarbenoids Derived from the Nucleophilic Desulfinylation of α-Chloro-α-fluoroalkyl Sulfoxides
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2-Aryl-1-chloro-1-fluoroethyl sulfoxides underwent nucleophilic desulfinylation with PhMgBr to give (Z)-fluorostyrene derivatives in a very stereoselective manner (>33:1) via an α-fluorocarbene species.When treated with 3 equiv of PhLi in the presence of N,N,N',N'-tetramethylethylenediamine, they similarly formed fluorostyrenes as a stereoisomeric mixture (E:Z = 2:1), but with 1 equiv of PhLi 1-aryl-1-chloro-1-fluoroethanes were the major product.On the other hand, no formation of a fluoroalkene was observed in the desulfinylation of 1-chloro-1-fluoro-4-phenylbutyl sul foxide with the nucleophiles.In the latter reaction, oxidation and/or phenylation of the intermediate carbene were the main pathways.
- Uno, Hidemitsu,Sakamoto, Katsuji,Semba, Fumihiko,Suzuki, Hitomi
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p. 210 - 217
(2007/10/02)
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