Five new secondary metabolites derived from pentanol, namely catathelasmols A-E (1-5), were isolated from the fruiting bodies of the basidiomycete Catathelasma imperiale. Their structures were elucidated on the basis of spectroscopic analysis, and the absolute configurations were determined by computational chemistry. Compounds 3, 4 and 5 showed inhibitory activities against two isozymes of 11b-hydroxysteroid dehydrogenases (11b-HSD1 and 11b-HSD2), with IC 50 values of 28.7-62.3 lg ml À1 (human 11b-HSD1), 30.4-149.2 lg ml À1 (mouse 11b-HSD1), 5.1-177 lg ml À1 (human 11b-HSD2) and 32.3-129.1 lg ml À1 (mouse 11b-HSD2), which catalyze the interconversion of cortisol and cortisone.