Oxidation of natural targets by dioxiranes. Part 6: on the direct regio- and site-selective oxyfunctionalization of estrone and of 5α-androstane steroid derivatives

• Published in: Tetrahedron letters Vol. 49; no. 39; pp. 5614 - 5617
• Main Authors: D’Accolti, Lucia, Fusco, Caterina, Lampignano, Giuditta, Capitelli, Francesco, Curci, Ruggero
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 22.09.2008; Elsevier
• Subjects: 5α-Androstane; Chemistry; Chemistry, Organic; Dioxiranes; Estrone; Hydroxylation; Methyl(trifluoromethyl)dioxirane; Physical Sciences; Regioselectivity; Science & Technology; Steroids; Dioxiranes; 5α-Androstane; Hydroxylation; Regioselectivity; Estrone; Methyl(trifluoromethyl)dioxirane; Steroids; regioselectivity; INSERTION; dioxiranes; hydroxylation; CONVERSION; CARBONS; 5 alpha-androstane; C-H BONDS; estrone; ALCOHOLS; methyl(trifluoromethyl)dioxirane; CHEMISTRY; steroids; INHIBITORS; EFFICIENT
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2008.07.042

Methyl(trifluoromethyl)dioxirane ( 1b) was employed to achieve under mild conditions the regio- and site selective direct synthesis of new oxyfunctionalized steroids 7 and 8. Using methyl(trifluoromethyl)dioxirane ( 1b), 3β,6α,17β-triacetoxy-5α-androstane ( 6) could be selectively transformed into its C-14 hydroxy derivative ( 7) and into the valuable C-12 ketone steroid ( 8), in high yields under mild reaction conditions. Similarly, the oxidation of 3α-estrone acetate ( 4) with 1b was carried out to yield selectively the steroid C-9 hydroxy derivative ( 5). The high regio- and site-selectivity attained demonstrates that the powerful dioxirane 1b is the reagent of choice to synthesize valuable oxyfunctionalized steroid derivatives.