The invention relates to 17α-(5-hydroxy-C5-hydrocarbyl)-1,3,5(10)-estratrien-3,17β-diol derivatives having cicatrising activity, preferably for topical use on wounds, without significant systemic effects, and to pharmaceutical compositions containing them. In particular, the invention relates to estradiol 17α-(5-hydroxypentyn-1-yl)derivatives and 3-esters, 5′-esters and 3,5′-diesters thereof and to a process for the preparation thereof by reaction of 3-OR-protected estrone with an alkali metal derivative of OR-protected 5-pentynol, followed by 3-, 5-′ or 3,5′-esterifÊcation.