Methods for the Stereoselective Synthesis of 2-Fluoroalkenoates. Carbonyl Condensation Reactions of 3,3-Bis(methylthio)-2-fluoropropenal, a Highly-Functionalized Fluoroacrylate Cation Equivalent

Article abstract of DOI:10.1021/jo00073a029

New methodology for the preparation of 2-fluoroacrylates has been developed on the basis of the reagent 3,3-bis(methylthio)-2-fluoropropenal.This highly-functionalized aldehyde is prepared by the condensation of carbon disulfide with fluoroacetonitrile followed by reduction of the nitrile.It is subjected to nucleophilic addition with organometallic reagents and enolates to yield allylic alcohol products that can be rearranged under acidic conditions to (Z)-2-fluoroacrylate thioesters.Other desired fluoroacrylates are also available via conventional fluorinated Horner-Wadsworth-Emmons or Reformatsky reagents.