Header

UZH-Logo

Maintenance Infos

Regio- and stereoselective reactions of a rhodanine derivative with optically active 2-methyl- and 2-phenyloxirane


Fu, Changchun; Thrane, Marie V; Linden, Anthony; Heimgartner, Heinz (2004). Regio- and stereoselective reactions of a rhodanine derivative with optically active 2-methyl- and 2-phenyloxirane. Tetrahedron, 60:5407-5412.

Abstract

The reaction of a rhodanine derivative (= (Z)-5-benzylidene-3-phenyl-2-thioxo-1,3-thiazolidin-4-one; 1) with (S)-2-methyl-oxirane (2) in the presence of SiO2 in dry CH2Cl2 for 10 days led to two diastereoisomeric spirocyclic 1,3-oxathiolanes 3 and 4 with the Me group at C(2) (Scheme 2). The analogous reaction of 1 with (R)-2-phenyloxirane (5) afforded also two diastereoisomeric spirocyclic 1,3-oxathiolanes 6 and 7 bearing the Ph group at C(3) (Scheme 3). The structures of 3, 4, 6, and 7 were confirmed by X-ray crystallography (Figs. 1 and 2). These results show that oxiranes react selectively with the thiocarbonyl group (C=S) in 1. Furthermore, the nucleophilic attack of the thiocarbonyl S-atom at the SiO2-activated oxirane ring proceeds with high regio- and stereoselectivity via an SN2-type mechanism.

Abstract

The reaction of a rhodanine derivative (= (Z)-5-benzylidene-3-phenyl-2-thioxo-1,3-thiazolidin-4-one; 1) with (S)-2-methyl-oxirane (2) in the presence of SiO2 in dry CH2Cl2 for 10 days led to two diastereoisomeric spirocyclic 1,3-oxathiolanes 3 and 4 with the Me group at C(2) (Scheme 2). The analogous reaction of 1 with (R)-2-phenyloxirane (5) afforded also two diastereoisomeric spirocyclic 1,3-oxathiolanes 6 and 7 bearing the Ph group at C(3) (Scheme 3). The structures of 3, 4, 6, and 7 were confirmed by X-ray crystallography (Figs. 1 and 2). These results show that oxiranes react selectively with the thiocarbonyl group (C=S) in 1. Furthermore, the nucleophilic attack of the thiocarbonyl S-atom at the SiO2-activated oxirane ring proceeds with high regio- and stereoselectivity via an SN2-type mechanism.

Statistics

Citations

8 citations in Web of Science®
8 citations in Scopus®
Google Scholar™

Altmetrics

Downloads

54 downloads since deposited on 14 Aug 2013
16 downloads since 12 months
Detailed statistics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2004
Deposited On:14 Aug 2013 14:09
Last Modified:05 Apr 2016 16:54
Publisher:Elsevier
ISSN:0040-4020
Funders:Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1016/j.tet.2004.04.066

Download

Preview Icon on Download
Content: Published Version
Filetype: PDF - Registered users only
Size: 210kB
View at publisher
Preview Icon on Download
Preview
Filetype: PDF
Size: 311kB