Abstract
Direct substitution and elimination reactions of the fluorine atoms of difluoromethylene CF2 alpha groups of nonspaced perfluoroalkyl chains, CF3 groups are very difficult to achieve. But, they become feasible with fluoro-alkenes, alkynes, imines or carbonyl derivatives, for which vinylic substitution and related carbanion-mediated pathways are available. In this review, we classify the major and unique fluorine substitution/elimination and rearrangement reactions and discuss their contribution to the synthesis of heterocyclic compounds.