Revision of the structure of 3-methoxy-14α-hydroxy-D-homo-1,3,5-(10)-estratrien-17a-one. A simple 1H NMR method for the determination of configuration of hydroxy group in position 5 and/or 14 of the D-homo-steroid skeleton

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Title:Revision of the structure of 3-methoxy-14α-hydroxy-D-homo-1,3,5-(10)-estratrien-17a-one. A simple 1H NMR method for the determination of configuration of hydroxy group in position 5 and/or 14 of the D-homo-steroid skeleton
Creators:
Buděšínský, Miloš
Kasal, Alexander
Procházka, Želimír
Thoa, Huynh Kim
Vašíčková, Soňa
Kočovský, Pavel
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 56, 7, pp. 1512-1524

Abstract

Eignerova and Prochazka found in 1974 the Cotton effect value for 3-methoxy-14α-hydroxy-D-homo-1,3,5(10)-estratrien-17a-one (<i>Ia</i>) to be Δε – 2.76.Calculation of the Δε value for this compound led, however, to a substantially lower value, which suggested the hypothesis that the compound was in fact rather an epimer with the hydroxy group in position 14β. This hypothesis was studied by means of <sup>1</sup>H NMR spectra of synthetic models, using the changes of the chemical shifts of angular methyls, induced by in situ acylation of the angular hydroxyl with an α- or β-configuration with trichloroacetyl isocyanate (TAI). The observed TAI-acylation shifts on model compounds indicated the structure <i>Ib</i> with a 14b-configuration of the hydroxyl group. Indenpendent proof has been given by the synthesis of both 14-hydroxy epimers, <i>Ia</i> and <i>Ib</i>. A simple <sup>1</sup>H NMR method is proposed for the determination of configuration of the hydroxyl in position 5 or 14 of D-homo-steroid skeleton.

Title:Revision of the structure of 3-methoxy-14α-hydroxy-D-homo-1,3,5-(10)-estratrien-17a-one. A simple 1H NMR method for the determination of configuration of hydroxy group in position 5 and/or 14 of the D-homo-steroid skeleton
Creators:
Buděšínský, Miloš
Kasal, Alexander
Procházka, Želimír
Thoa, Huynh Kim
Vašíčková, Soňa
Kočovský, Pavel
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:56
Number:7
Page Range:pp. 1512-1524
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19911512UNSPECIFIED
ID Code:5074
Item Type:Article
Deposited On:22 Feb 2010 11:29
Last Modified:22 Feb 2010 10:30

Citation

Buděšínský, Miloš; Kasal, Alexander; Procházka, Želimír; Thoa, Huynh Kim; Vašíčková, Soňa; Kočovský, Pavel (1991) Revision of the structure of 3-methoxy-14α-hydroxy-D-homo-1,3,5-(10)-estratrien-17a-one. A simple 1H NMR method for the determination of configuration of hydroxy group in position 5 and/or 14 of the D-homo-steroid skeleton. Collection of Czechoslovak Chemical Communications, 56 (7). pp. 1512-1524. ISSN 0010-0765

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