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Abstract In the present article an attempt is made to summarize the steric requirements and the influence of neighboring groups which determine the course of intramolecular radical reactions. Steroids are used as substrates for these reactions, since here the spatial arrangement of the ring members and the distances between substituents are largely fixed. Furthermore, intramolecular free‐radical reactions are of practical importance in steroid chemistry in connection with substitution at non‐activated carbon atoms. Almost all the reactions discussed begin with the formation of an oxygen radical by oxidation of an alcohol with lead tetraacetate or by homolysis of the corresponding hypoiodite.
Heusler et al. (Sat,) studied this question.