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Metalloporphyrins efficiently catalyze the epoxidation reactions of 17\u03b2\u2010acetoxy\u20104\u2010androstene (<jats:bold>1<\/jats:bold>), 4\u2010cholestene (<jats:bold>2<\/jats:bold>) and 3\u03b2\u2010acetoxy\u20105\u2010cholestene (<jats:bold>3<\/jats:bold>) in the presence of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> as oxygen donor. Modeling the molecular structure of the porphyrin as well as the central metal allows the control of the preferential formation of \u03b1\u2010 or \u03b2\u2010epoxides. Porphyrins with bulky, electron\u2010withdrawing groups in the <jats:italic>ortho <\/jats:italic>positions of the <jats:italic>meso<\/jats:italic> phenyls and with Mn<jats:sup>III<\/jats:sup> as the central metal ion, such as [Mn(TDCPP)Cl], gave preferentially the \u03b2\u2010epoxide of \u0394<jats:sup>4<\/jats:sup>\u2010 and \u0394<jats:sup>5<\/jats:sup>\u2010steroids. [Fe(TPFPP)Cl] catalyzes preferentially the \u03b1\u2010epoxidation of \u0394<jats:sup>4<\/jats:sup>\u2010steroids and also increases the stereoselectivity for the \u03b1\u2010epoxide in \u0394<jats:sup>5<\/jats:sup>\u2010steroids, similar to the results obtained with <jats:italic>m<\/jats:italic>\u2010CPBA (<jats:italic>m<\/jats:italic>\u2010chloroperbenzoic acid) as oxidant. The substrate structure strongly influences the chemoselectivity of the reactions. The X\u2010ray structures of two main products were determined, and two\u2010dimensional NMR techniques allowed the full assignment of <jats:sup>1<\/jats:sup>H and <jats:sup>13<\/jats:sup>C NMR resonances as well as the stereochemistry of these products. A mechanistic proposal involving oxo species for the \u03b2\u2010approach and peroxy species for the \u03b1\u2010approach is proposed. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2004)<\/jats:p>","DOI":"10.1002\/ejoc.200400461","type":"journal-article","created":{"date-parts":[[2004,11,15]],"date-time":"2004-11-15T10:48:49Z","timestamp":1100515729000},"page":"4778-4787","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Oxidation of \u0394<sup>4<\/sup>\u2010 and \u0394<sup>5<\/sup>\u2010Steroids with Hydrogen Peroxide Catalyzed by Porphyrin Complexes of Mn<sup>III<\/sup> and Fe<sup>III<\/sup>"],"prefix":"10.1002","volume":"2004","author":[{"given":"Susana\u00a0L.\u00a0H.","family":"Rebelo","sequence":"first","affiliation":[]},{"given":"M\u00e1rio\u00a0M.\u00a0Q.","family":"Sim\u00f5es","sequence":"additional","affiliation":[]},{"given":"M.\u00a0Gra\u00e7a\u00a0P.\u00a0M.\u00a0S.","family":"Neves","sequence":"additional","affiliation":[]},{"given":"Artur\u00a0M.\u00a0S.","family":"Silva","sequence":"additional","affiliation":[]},{"given":"Jos\u00e9\u00a0A.\u00a0S.","family":"Cavaleiro","sequence":"additional","affiliation":[]},{"given":"Andreia\u00a0F.","family":"Peixoto","sequence":"additional","affiliation":[]},{"given":"Mariette\u00a0M.","family":"Pereira","sequence":"additional","affiliation":[]},{"given":"Manuela\u00a0R.","family":"Silva","sequence":"additional","affiliation":[]},{"given":"Jos\u00e9\u00a0A.","family":"Paix\u00e3o","sequence":"additional","affiliation":[]},{"given":"Ana\u00a0M.","family":"Beja","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,11,15]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"P. 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