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Reaction of Thioketones with (R)-2-Vinyloxirane: Regio- and Stereoselective Formation of (S)-4-Vinyl-1,3-oxathiolanes


Fedorov, Alexey; Fu, Changchun; Linden, Anthony; Heimgartner, Heinz (2005). Reaction of Thioketones with (R)-2-Vinyloxirane: Regio- and Stereoselective Formation of (S)-4-Vinyl-1,3-oxathiolanes. European Journal of Organic Chemistry:1613-1619.

Abstract

The reactions of 4,4-dimethoxythiobenzophenone (1), 9H-xanthene- 9-thione (2), and adamantane-2-thione (3) with (R)-2-vinyloxirane [(R)-6] in the presence of SiO2 in anhydrous CH2Cl2 at 0 °C or room temperature afforded the corresponding 4-vinyl-1,3-oxathiolane derivatives (S)-7, (S)-9, and (S)-11, respectively. The analogous BF3-catalyzed reactions of (R)-6 with 1,1,3,3-tetramethylindane-2-thione (4) and 2,2,4,4-tetramethyl-3-thioxocyclobutanone (5) in anhydrous CH2Cl2 at –65 °C or –78 °C yielded the corresponding spirocyclic 1,3-oxathiolanes (S)-12 and (S)-14, respectively. The structures of (S)-9 and (S)-12 were established by X-ray crystallography. In all cases, the nucleophilic thiocarbonyl S atom attacked predominantly C(2) of the Lewis acid-activated (R)-2-vinyloxirane ring with inversion of the configuration through an SN2-type mechanism

Abstract

The reactions of 4,4-dimethoxythiobenzophenone (1), 9H-xanthene- 9-thione (2), and adamantane-2-thione (3) with (R)-2-vinyloxirane [(R)-6] in the presence of SiO2 in anhydrous CH2Cl2 at 0 °C or room temperature afforded the corresponding 4-vinyl-1,3-oxathiolane derivatives (S)-7, (S)-9, and (S)-11, respectively. The analogous BF3-catalyzed reactions of (R)-6 with 1,1,3,3-tetramethylindane-2-thione (4) and 2,2,4,4-tetramethyl-3-thioxocyclobutanone (5) in anhydrous CH2Cl2 at –65 °C or –78 °C yielded the corresponding spirocyclic 1,3-oxathiolanes (S)-12 and (S)-14, respectively. The structures of (S)-9 and (S)-12 were established by X-ray crystallography. In all cases, the nucleophilic thiocarbonyl S atom attacked predominantly C(2) of the Lewis acid-activated (R)-2-vinyloxirane ring with inversion of the configuration through an SN2-type mechanism

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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:2005
Deposited On:07 Dec 2012 15:19
Last Modified:05 Apr 2016 16:07
Publisher:Wiley-Blackwell
ISSN:1099-0690
Funders:Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/ejoc.200400766
Related URLs:http://onlinelibrary.wiley.com/journal/10.1002/%28ISSN%291099-0690 (Publisher)

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