Addition reactions of perfluoroalkyl radicals to ordinary or polyfluorinated alkenes have been frequently used to synthesize perfluoroalkylated organic compounds. Here ethyl/methyl 2-bromo-2,2-difluoroacetate, diethyl (bromodifluoromethyl)phosphonate, [(bromodifluoromethyl)sulfonyl]benzene, and ethyl 2-bromo-2-fluoroacetate were involved in Na2S2O4-mediated radical additions to vinyl ethers in the presence of alcohols to give difluoro or monofluoroacetyl-substituted acetals or corresponding difluoromethylphosphonate- and (difluoromethylphenyl)sulfonyl-substituted alkyl acetals. This methodology has also been applied as a key step in the synthesis of hitherto unknown 3,3-difluoro-GABA, completing the series of isomeric difluoro GABAs. Comparison of the pKa values of 3-fluoro- and 3,3-difluoro-GABA with that of the fluorine free parent compound showed that introduction of each fluorine lead to acidification of both the amino and the carboxyl functions by approximately one unit.

Radical Reactions of Alkyl 2-Bromo-2,2-difluoroacetates with Vinyl Ethers: “Omitted” Examples and Application for the Synthesis of 3,3-Difluoro-GABA

Synthesis of 2,3- or 1,2-unsaturated derivatives of 2-deoxy-2-trifluoromethylhexopyranoses

Studies on sulfinatodehalogenation XIII: Synthesis of 2- perfluoroalkyl-2-deoxy-D-glucose, mono-and poly-O- polyfluoroalkylated-D-glucoses

Organofluorine Compounds and Fluorinating Agents. Part 30. A Common Sugar as Model for Many-Sided Natural Product Modification. From D-Fructose via D-Tagatose to 2-C-Chlorodifluoro-methylated D-Arabinopyranos-5-ulose Derivatives.

A Common Sugar as Model for Many‐Sided Natural Product Modification. From D‐Fructose via D‐Tagatose to 2‐C‐Chlorodifluoro‐methylated D‐Arabinopyranos‐5‐ulose Derivatives

Arun K. Shaw

Papers

A Common Sugar as Model for Many‐Sided Natural Product Modification. From D‐Fructose via D‐Tagatose to 2‐C‐Chlorodifluoro‐methylated D‐Arabinopyranos‐5‐ulose Derivatives

Organofluorine Compounds and Fluorinating Agents. Part 30. A Common Sugar as Model for Many-Sided Natural Product Modification. From D-Fructose via D-Tagatose to 2-C-Chlorodifluoro-methylated D-Arabinopyranos-5-ulose Derivatives.