کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
10848129 1070650 2005 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Oxidative chemistry of 2-nitro and 4-nitroestradiol: Dichotomous behavior of radical intermediates and novel potential routes for oxyfunctionalization and B-ring fission of steroidal scaffolds
موضوعات مرتبط
علوم زیستی و بیوفناوری بیوشیمی، ژنتیک و زیست شناسی مولکولی زیست شیمی
پیش نمایش صفحه اول مقاله
Oxidative chemistry of 2-nitro and 4-nitroestradiol: Dichotomous behavior of radical intermediates and novel potential routes for oxyfunctionalization and B-ring fission of steroidal scaffolds
چکیده انگلیسی
Oxidation of 4-nitro-17β-estradiol (1) with the peroxidase/H2O2 system gave the symmetric C2-linked dimer (3) through phenoxy radical coupling. Similar oxidation of 2-nitro-17β-estradiol (2), in which the nitro group is coplanar with the aromatic ring, yielded 9α- and 9β-hydroxy-2-nitro-17β-estradiol (4a,b), (17β)-2-nitroestra-1(10),2,4,9(11)-tetraene-3,17-diol (5), and (12α,17β)-2-nitroestra-1(10),2,4,9(11)-tetraene-3,12,17-triol (6). With higher concentrations of H2O2, the novel secoestra-1(10),2,4-trien-9-one derivative 7 was obtained from 2. Theoretical calculations suggested that the peculiar behavior of 2 may be due to the generation of a relatively stable radical intermediate at C9, which would then be converted to the reactive quinone methide 8. The chemistry described in this paper appears to be an intriguing example of control of the site of substitution over evolution of phenoxy radicals, and opens new vistas toward selective oxyfunctionalization of the estrane skeleton.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Steroids - Volume 70, Issue 8, July 2005, Pages 543-550
نویسندگان
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