Radical Addition of Carboxylic Acids and Carboxylic Acid Derivatives to Unsaturated Compounds as a Synthetic Method

After a brief discussion of the mechanism of radical additions to olefins and of possibilities for initiating the radical chain, the reaction is described as a synthetic method for the preparation of carboxylic acid derivatives. Selected preparative procedures and tables with preparative data indicate the breadth of applicability of the method. The unsaturated compounds: open-chain, cyclic, or bicyclic unsubstituted and substituted olefins, and also dienes and alkynes, can be subjected to free-radical reaction under various conditions with simple and substituted mono- and dicarboxylic acid derivatives as well as with tricarboxylic acid esters. Free acids, esters, lactones, amides, lactams, anhydrides, nitriles, and acid chlorides, and also α-amino-acid derivatives as well as α-halo acids undergo addition reactions with olefins if at least one hydrogen or halogen atom is located on the α- atom of the acid or acid derivative. The dependence of the yields of 1:1 adduct on the reaction parameters in noted and possibilites of an addition which is selective for α-olefins are described.