Stereochemical course of the hydroboration of highly hindered steroidal olefins. A ready synthesis of 14 beta- and 8 alpha,14 beta-steroids.

Hydroboration of 5 alpha-cholest-8-ene, 5 alpha,14 beta-cholest-8-ene and 5 alpha,14 beta-cholest-7-ene provides a simple route to oxygenated steroids with 14 beta- and 8 alpha,14 beta- unnatural stereochemistry.

A convenient isomerization of 6-oxo-3 alpha,5-cyclo-5 alpha-steroids to 6-oxo-delta 2-5 alpha-steroids.

Direct isomerization of 6-oxo-3 alpha,5-cyclo-5 alpha-steroids to 6-oxo-delta 2-5 alpha-steroids was accomplished by pyridinium hydrobromide in dimethyl-formamide.