3.alpha.-Hydroxy and 3.alpha.-acyloxy- .DELTA..sup.9(11) -5.alpha.-20-ketopregnenes of the formula ##STR1## wherein R is hydrogen or acyl, R.sub.1 is hydrogen or methyl and R.sub.2 is methyl or ethyl, are produced by esterifying a corresponding 3.beta.-hydroxy-5.alpha.-20-keto pregnane of the formula ##STR2## wherein R.sub.1 and R.sub.2 have the values given above, with m-iodobenzoic acid with inversion of the 3.beta.-oxy group to a 3.alpha.-oxy group; chlorinating the thus-produced 3.alpha.-m-iodobenzoyl ester with dichloroiodobenzene under irradiation; and treating the reaction product with a dehydrohalogenating silver salt. Optionally thereafter, the 3.alpha.-iodobenzoyl group is split off in a conventional manner to produce the corresponding 3.alpha.-hydroxy steroid and optionally the thus-produced 3.alpha.-hydroxy steroid is esterified to produce a desired 3-ester thereof.