The chemistry of the steroid 17@-carboxylic acids derived from 16, 17a-disubstituted corticosteroids was investigated with respect to thiol ester formation. Major quantities of 17- spiro byproducts were observed in the reactions of 16-methyl-17a-acyloxy acids, and the degree of 17-ester participation leading to these structures was dependent on the carboxylate activating group used and stereochemistry at C-16. Diethyl phosphate mixed ...