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Reactions of Sulfanyl Chlorides with Thiocamphor and Thiofenchone: Wagner-Meerwein Rearrangement of an Intermediate Thiocarbonylium Ion


Majchrzak, Agnieszka; Mloston, Grzegorz; Linden, Anthony; Heimgartner, Heinz (2004). Reactions of Sulfanyl Chlorides with Thiocamphor and Thiofenchone: Wagner-Meerwein Rearrangement of an Intermediate Thiocarbonylium Ion. Helvetica Chimica Acta, 87:790-799.

Abstract

The reaction of sulfanyl and disulfanyl chlorides with thiocamphor (6) in the presence of Et3N leads to unsymmetrical di- and trisulfanes, respectively (Schemes 2 and 4). A reaction mechanism via a thiocarbonylium ion, which is immediately deprotonated, is proposed. The formation of a minor product 10 in the absence of a base, resulting from a Wagner-Meerwein rearrangement, is an additional evidence for the intermediacy of a thiocarbonylium ion (Scheme 3). On the other hand, the non-enolizable thiofenchone (13) reacts with sulfanyl chlorides in CH2Cl2/Et3N to give exclusively products with a rearranged bicyclic skeleton (Scheme5). A Wagner-Meerwein rearrangement of the intermediate thiocarbonylium ion is the key step. The structures of the products 10 and 14, which have rearranged bicyclic systems, have been established by X-ray crystallography.

Abstract

The reaction of sulfanyl and disulfanyl chlorides with thiocamphor (6) in the presence of Et3N leads to unsymmetrical di- and trisulfanes, respectively (Schemes 2 and 4). A reaction mechanism via a thiocarbonylium ion, which is immediately deprotonated, is proposed. The formation of a minor product 10 in the absence of a base, resulting from a Wagner-Meerwein rearrangement, is an additional evidence for the intermediacy of a thiocarbonylium ion (Scheme 3). On the other hand, the non-enolizable thiofenchone (13) reacts with sulfanyl chlorides in CH2Cl2/Et3N to give exclusively products with a rearranged bicyclic skeleton (Scheme5). A Wagner-Meerwein rearrangement of the intermediate thiocarbonylium ion is the key step. The structures of the products 10 and 14, which have rearranged bicyclic systems, have been established by X-ray crystallography.

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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:2004
Deposited On:14 Aug 2013 13:13
Last Modified:05 Apr 2016 16:54
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel, olish State Committee for Scientific Research (grant No. 4 T09A 046 25)
Publisher DOI:https://doi.org/10.1002/hlca.200490077

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