Proton and carbon-13 nuclear magnetic resonance spectroscopy of diastereoisomeric 3- and 17β-tetrahydropyranyl ether derivatives of estrone and estradiol
Protection of 3- and 17β-hydroxyl groups of estrone and estradiol as tetrahydropyranyl ether derivatives led to mixtures of 2'(R)- and 2'(S)-diastereoisomers which were separated by crystallization (3-tetrahydropyranyl ethers), or by thin-layer chromatography (17-tetrahydropyranyl ethers),...
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Published in | Steroids Vol. 55; no. 5; pp. 209 - 221 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
United States
Elsevier Inc
01.05.1990
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Subjects | |
Online Access | Get full text |
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Summary: | Protection of 3- and 17β-hydroxyl groups of estrone and estradiol as tetrahydropyranyl ether derivatives led to mixtures of 2'(R)- and 2'(S)-diastereoisomers which were separated by crystallization (3-tetrahydropyranyl ethers), or by thin-layer chromatography (17-tetrahydropyranyl ethers), and characterized by
1H and
13C nuclear magnetic resonance (NMR). Assignments for NMR signals of estradiol 3,17β-ditetrahydropyranyl ether were facilitated by comparison with those of its 15ξ,16ξ-dideuterio analog and by 2D
1H-
13C heteroshift correlation experiments. Diastereoisomers of 3-tetrahydropyranyl ether derivatives could be identified through the
13C NMR doublet signals of the anomeric C-2' and the aromatic C-4 carbon atoms in cdcl
3 . Diastereoisomers of 17-tetrahydropyranyl ether derivatives were recognized from characteristic modifications of
1H NMR signals of H-2', H-6', H-1, H-17, and 18-CH
3 protons as well as from the
13C NMR doublet signals corresponding to C-2', C-4', C-6', C-12, C-13, C-16, and C-17 carbon atoms. Low-temperature experiments showed a splitting of the C-2', C-6', and C-17
13C NMR signals of each of the two 17-tetrahydropyranyl ether isomers. The downfield signal (equatorial conformer) of the three resulting doublets was more intense for the 17-tetrahydropyranyl ether 2'(S)-isomer, whereas the upfield signal (axial conformer) was more intense for the 2'(R)-isomer. (Steroids
55:209–221, 1990). |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0039-128X 1878-5867 |
DOI: | 10.1016/0039-128X(90)90018-7 |