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Reactivity of Steroidal Dienes towards the Methyltrioxorhenium/H 2 O 2 −Urea Oxidation System: Isolation and Characterization of New Oxygenated Steroids
Author(s) -
Sica Donato,
Musumeci Domenica,
Zollo Franco,
De Marino Simona
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200110)2001:19<3731::aid-ejoc3731>3.0.co;2-2
Subject(s) - chemistry , reactivity (psychology) , adduct , diene , pyridine , organic chemistry , steroid , conjugated system , medicinal chemistry , ether , hydrogen peroxide , medicine , alternative medicine , pathology , biochemistry , natural rubber , hormone , polymer
To examine the reactivity of conjugated diene steroids towards methyltrioxorhenium (MTO)‐catalysed oxidation with the urea−hydrogen peroxide adduct (UHP) and its possible use in functionalization of the rings of the steroid nucleus, the reactions of the MTO/UHP system with cholesta‐3,5‐diene ( 4 ) and 5α‐cholesta‐7,9(11)‐dien‐3β‐yl acetate ( 13 ) in aprotic solvents were investigated. These oxidations were performed both at 0 °C and at 25 °C, in either CHCl 3 or diethyl ether as solvents, and in the presence of pyridine as ligand. Three new 4,5‐epoxy‐3,6‐dihydroxyl compounds 10 , 11 , and 12 were isolated from the treatment of diene 4 in CHCl 3 at 0 °C, while oxidations of the Δ 7,9(11) ‐diene steroid 13 allowed us to isolate the new monoepoxy and diepoxy steroids 14 and 15 and the new triol 19 . The structures of all new steroids were verified on the basis of chemical evidence and interpretation of spectroscopic data including H‐H COSY, HMBC, and HMQC experiments.