Header

UZH-Logo

Maintenance Infos

Regio- and stereoselective 1,3-Oxathiolane formation in the reaction of Thiolactones with optically active oxiranes


Fu, Changchun; Linden, Anthony; Heimgartner, Heinz (2004). Regio- and stereoselective 1,3-Oxathiolane formation in the reaction of Thiolactones with optically active oxiranes. Helvetica Chimica Acta, 87(9):2296-2309.

Abstract

The reactions of 3H-isobenzofuran-1-thione (1) with (S)-2-methyloxirane (2) and (R)-2-phenyloxirane (6) in the presence of SiO2 in anhydrous CH2Cl2 led to two pairs of diastereoisomeric spirocyclic 1,3-oxathiolanes, i.e., 3 and 4 with a Me group at C(5'), and 7 and 8 with a Ph group at C(4'), respectively (Schemes 2 and 3). In both cases, 3H-isobenzofuran-1-one (5) was formed as a main product. The analogous reactions of 3,4-dihydro-2H-[1]benzopyran-2-thione (9) and 3,4,5,6-tetrahydro-2H-pyran-2-thione (14) with 2 and 6 yielded four pairs of the corresponding diastereoisomeric spirocyclic compounds 10 and 11, 12 and 13, 15 and 16, and 18 and 19, respectively (Schemes 4 - 7). In the reaction of 14 with 6, the 1,3-oxathiolane 20 with a Ph group at C(2) was also formed. The structures of 3, 7, 8, 10, 19, and 20 were established by X-ray crystallography (Figs.1-4). In contrast to the thiolactones 1, 9, and 14, the thioesters 21a-21d did not react with (R)-2-phenyloxirane (6) either in the presence of SiO2 or under more-drastic conditions with BF3 . Et2O or SnCl4 (Scheme 8). The results show that spirocyclic 1,3-oxathiolanes can be prepared from thiolactones with oxiranes. 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 reactions of 3H-isobenzofuran-1-thione (1) with (S)-2-methyloxirane (2) and (R)-2-phenyloxirane (6) in the presence of SiO2 in anhydrous CH2Cl2 led to two pairs of diastereoisomeric spirocyclic 1,3-oxathiolanes, i.e., 3 and 4 with a Me group at C(5'), and 7 and 8 with a Ph group at C(4'), respectively (Schemes 2 and 3). In both cases, 3H-isobenzofuran-1-one (5) was formed as a main product. The analogous reactions of 3,4-dihydro-2H-[1]benzopyran-2-thione (9) and 3,4,5,6-tetrahydro-2H-pyran-2-thione (14) with 2 and 6 yielded four pairs of the corresponding diastereoisomeric spirocyclic compounds 10 and 11, 12 and 13, 15 and 16, and 18 and 19, respectively (Schemes 4 - 7). In the reaction of 14 with 6, the 1,3-oxathiolane 20 with a Ph group at C(2) was also formed. The structures of 3, 7, 8, 10, 19, and 20 were established by X-ray crystallography (Figs.1-4). In contrast to the thiolactones 1, 9, and 14, the thioesters 21a-21d did not react with (R)-2-phenyloxirane (6) either in the presence of SiO2 or under more-drastic conditions with BF3 . Et2O or SnCl4 (Scheme 8). The results show that spirocyclic 1,3-oxathiolanes can be prepared from thiolactones with oxiranes. 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

5 citations in Web of Science®
7 citations in Scopus®
Google Scholar™

Altmetrics

Downloads

37 downloads since deposited on 13 Aug 2013
9 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:13 Aug 2013 14:55
Last Modified:05 Apr 2016 16:54
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/hlca.200490205

Download

Preview Icon on Download
Preview
Content: Accepted Version
Filetype: PDF
Size: 925kB
View at publisher
Preview Icon on Download
Content: Published Version
Filetype: PDF - Registered users only
Size: 345kB