The synthesis of substituted tetrahydrothiophenes by rearrangement of 4-alkenylthiazolidin-2-ones
The synthesis of substituted tetrahydrothiophenes by rearrangement of 4-alkenylthiazolidin-2-ones
A review is presented of the important natural and semi-synthetic tetra hydrothiophenes together with the general methods which have been developed for the synthesis of tetrahydrothiophenes. In addition, the syntheses of the vitamin biotin which contains a trisubstituted tetrahydrothiophene ring have been reviewed. A number of deficiencies in these syntheses have been highlighted and a new route to substituted tetrahydrothiophenes via the rearrangement of 4-alkenylthiazolidin-2-ones with N-bromosuccinimide has been investigated.
It has been shown that 3-bromo-4-isocyanatotetrahydrothiophene which results from the rearrangement of 4-vinythiazolidin-2-one may be trapped with a number of amines to give the corresponding bromo ureas which may be isolated as single isomers. Alternatively, trappings of the above isocyanate with alcohols gave the corresponding carbamates as mixtures of isomers which in certain cases have been separated.
A synthesis of cis-tetrahydro-l,3-bis(phenylmethyl)-lH-thieno[3,4-d]imidazol-2(3H)-one, a reported and characterised diaminosubstituted tetra-hydrothiophene was undertaken and completed starting from the rearrangement of 4-vinylthiazolidin-2-onc. This synthesis constitutes a formal synthesis of the vitamin biotin and proves that cis substituted tetra-hydrothiophenes may be synthesised via this arrangement. Some bromo ureas and bromo carbamates described in this thesis have been related to compounds of known configuration described in the literature. Hence by relation to known compounds stereochcmical assignments have been made. Support for these assignments has been obtained by detailed spectroscopic analysis of a pair of isomeric azido substituted tctrahydrothiophencs which were synthesised from the corresponding bromides. To extend the utility of this thiazolidin-2-one rearrangement towards a synthesis of 2,3,4-trisubstituted tctrahydrothiophenes a number of 4-alkenyl-thiazolidin-2-ones have been prepared in raccmic form starting from 1,4-dichlorobut-2-ene or l,4-dibromo-2-mcthylbut-2-ene and in chi-ral form from L-cysteine ethyl ester hydrochloridc. Treatment of these 4-alkenyl-thiazolidin-2-ones with N-bromosuccinimide led to the isolation of a number of 2,3,4-trisubstituted tctrahydrothiophenes.
University of Southampton
1991
Jennings, David Ian
(1991)
The synthesis of substituted tetrahydrothiophenes by rearrangement of 4-alkenylthiazolidin-2-ones.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
A review is presented of the important natural and semi-synthetic tetra hydrothiophenes together with the general methods which have been developed for the synthesis of tetrahydrothiophenes. In addition, the syntheses of the vitamin biotin which contains a trisubstituted tetrahydrothiophene ring have been reviewed. A number of deficiencies in these syntheses have been highlighted and a new route to substituted tetrahydrothiophenes via the rearrangement of 4-alkenylthiazolidin-2-ones with N-bromosuccinimide has been investigated.
It has been shown that 3-bromo-4-isocyanatotetrahydrothiophene which results from the rearrangement of 4-vinythiazolidin-2-one may be trapped with a number of amines to give the corresponding bromo ureas which may be isolated as single isomers. Alternatively, trappings of the above isocyanate with alcohols gave the corresponding carbamates as mixtures of isomers which in certain cases have been separated.
A synthesis of cis-tetrahydro-l,3-bis(phenylmethyl)-lH-thieno[3,4-d]imidazol-2(3H)-one, a reported and characterised diaminosubstituted tetra-hydrothiophene was undertaken and completed starting from the rearrangement of 4-vinylthiazolidin-2-onc. This synthesis constitutes a formal synthesis of the vitamin biotin and proves that cis substituted tetra-hydrothiophenes may be synthesised via this arrangement. Some bromo ureas and bromo carbamates described in this thesis have been related to compounds of known configuration described in the literature. Hence by relation to known compounds stereochcmical assignments have been made. Support for these assignments has been obtained by detailed spectroscopic analysis of a pair of isomeric azido substituted tctrahydrothiophencs which were synthesised from the corresponding bromides. To extend the utility of this thiazolidin-2-one rearrangement towards a synthesis of 2,3,4-trisubstituted tctrahydrothiophenes a number of 4-alkenyl-thiazolidin-2-ones have been prepared in raccmic form starting from 1,4-dichlorobut-2-ene or l,4-dibromo-2-mcthylbut-2-ene and in chi-ral form from L-cysteine ethyl ester hydrochloridc. Treatment of these 4-alkenyl-thiazolidin-2-ones with N-bromosuccinimide led to the isolation of a number of 2,3,4-trisubstituted tctrahydrothiophenes.
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Published date: 1991
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Local EPrints ID: 460383
URI: http://eprints.soton.ac.uk/id/eprint/460383
PURE UUID: 02d7d045-a837-4ccb-9d5e-b8fa9cde5918
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Date deposited: 04 Jul 2022 18:21
Last modified: 04 Jul 2022 18:21
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Author:
David Ian Jennings
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