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Synthesis and structural characterization of the isomuscarines

Kempter, Irina and Frensch, Britta and Kopf, Thomas and Kluge, Ralph and Csuk, René and Svoboda, Ingrid and Fuess, Hartmut and Hartung, Jens (2014):
Synthesis and structural characterization of the isomuscarines.
In: Tetrahedron, 70 (10), Elsevier Science Publishing, pp. 1918-1927, ISSN 00404020,
[Online-Edition: http://dx.doi.org/10.1016/j.tet.2013.12.085],
[Article]

Abstract

Four diastereomers of 2-[(trimethylammonium)-methyl]-5-methyltetrahydrofuran-3-ol, trivially named isomuscarine, allo-isomuscarine, epi-isomuscarine, and epiallo-isomuscarine, were prepared as bromide salts from 2,4-like and 2,4-unlike diastereomers of 3-(4-hydroxyhex-5-en-2-oxy)-4-methylthiazole-2(3H)-thione. The strategy for constructing the tetrahydrofuran nucleus of the isomuscarines uses alkenoxyl radical 5-exo-bromocyclization, occurring 2,3-cis-selectively for the 2,4-like-4-hydroxyhex-5-en-2-oxyl radical, and 2,3-trans-selectively for the 2,4-unlike diastereomer. A fraction of 4-hydroxyhex-5-en-2-oxyl radicals cyclizes 6-endo-selectively providing 5-bromo-2-methyltetrahydropyran-4-ols in yields between 3 and 15%. Substituting trimethylamine for bromide in 5-exo-bromocyclized products furnishes isomuscarine bromides, which were structurally characterized by X-ray diffraction and NMR-spectroscopy.

Item Type: Article
Erschienen: 2014
Creators: Kempter, Irina and Frensch, Britta and Kopf, Thomas and Kluge, Ralph and Csuk, René and Svoboda, Ingrid and Fuess, Hartmut and Hartung, Jens
Title: Synthesis and structural characterization of the isomuscarines
Language: English
Abstract:

Four diastereomers of 2-[(trimethylammonium)-methyl]-5-methyltetrahydrofuran-3-ol, trivially named isomuscarine, allo-isomuscarine, epi-isomuscarine, and epiallo-isomuscarine, were prepared as bromide salts from 2,4-like and 2,4-unlike diastereomers of 3-(4-hydroxyhex-5-en-2-oxy)-4-methylthiazole-2(3H)-thione. The strategy for constructing the tetrahydrofuran nucleus of the isomuscarines uses alkenoxyl radical 5-exo-bromocyclization, occurring 2,3-cis-selectively for the 2,4-like-4-hydroxyhex-5-en-2-oxyl radical, and 2,3-trans-selectively for the 2,4-unlike diastereomer. A fraction of 4-hydroxyhex-5-en-2-oxyl radicals cyclizes 6-endo-selectively providing 5-bromo-2-methyltetrahydropyran-4-ols in yields between 3 and 15%. Substituting trimethylamine for bromide in 5-exo-bromocyclized products furnishes isomuscarine bromides, which were structurally characterized by X-ray diffraction and NMR-spectroscopy.

Journal or Publication Title: Tetrahedron
Volume: 70
Number: 10
Publisher: Elsevier Science Publishing
Uncontrolled Keywords: Alkoxyl radical, Bromocyclization, Muscarine alkaloid, Stereoselective synthesis, Tetrahydrofuran, Thiazolethione
Divisions: 11 Department of Materials and Earth Sciences > Material Science > Structure Research
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences
Date Deposited: 23 Jan 2015 09:04
Official URL: http://dx.doi.org/10.1016/j.tet.2013.12.085
Identification Number: doi:10.1016/j.tet.2013.12.085
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