Syntheses with perfluoroalkyl radicals from perfluoroalkyl iodides. A rapid survey of synthetic possibilities with emphasis on practical applications. Part one: Alkenes, alkynes and allylic compounds

This review concerns the free radical chemistry of perfluoroalkyl iodides (RFI) in the synthesis of organic substances of a large variety of structures. Radical chain reactions of RFI are readily initiated by azonitrile initiators and this process generally gives pure products from unsaturated compounds of many types; the process is called iodoperfluoroalkylation. In the synthesis of fluorine containing organic compounds, few methods can compare with the efficiency, cost, selectivity and versatility of free radical addition of RFI. Part one reviews all aspects of the generation of R-F radicals from RFI for synthetic purposes and reports the relative reactivity of RFI and of 20 typical alkenes or alkynes. Practical syntheses of 16 different classes of alkenes and alkynes are illustrated by examples and comprehensive tables of experimental data. Special emphasis is given to novel and important uses for many of these new perfluoroalkyl-substituted compounds. The aim of this review is to bring together in one place the results of research with RFI as an entry into the synthesis of fluorine containing organic compounds, over a fifty year time span. Additional classes of compounds are treated in subsequent parts of this review. (C) 1999 Elsevier Science S.A. All rights reserved.