Steroids and related products. XLIII. The synthesis of 17-hydroxymethylprogesterone

The synthesis of the first 17-hydroxymethyl analogue of a steroid hormone of the progesterone-corticoid group, 17-hydroxymethylprogesterone, is described. The starting material for its preparation was 3alpha,12alpha-diacetoxy-5beta-pregnan-20-one and the 17-hydroxymethyl structure was developed by functionalization of the 17-methyl group of a 17alpha-methyl etio ester by a Barton reaction. Neither 17-hydroxymethylprogesterone nor its acetate shows appreciable progestational activity in the Clauberg-McPhail assay.