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Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles


Majchrzak, A; Mloston, G; Linden, A; Heimgartner, H (2006). Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles. Helvetica Chimica Acta, 89(5):1042-1061.

Abstract

The reactions of 3-chloro-3-(chlorosulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (2) with N, O, S, and P nucleophiles occur by substitution of Cl at the S-atom. Whereas, in the cases of secondary amines, alkanols, phenols, thiols, thiophenols, and di- and trialkyl phosphates, the initially formed substitution
products were obtained, the corresponding products with allyl and propargyl alcohols undergo a [2,3]-sigmatropic rearrangement to give allyl and allenyl sulfoxides, respectively. Analogous substitution reactions were observed when 3-chloro-3-(chlorodisulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (3) was treated with N, O, and S nucleophiles. The reaction of 3 with Et3P led to an unexpected product via cleavage of the S S bond (cf. Scheme 13). In the reactions of 2 with primary amines and H2O, the substitution products react further via elimination of HCl to yield the corresponding thiocarbonyl S-imides and the thiocarbonyl S-oxide, respectively. Whereas the latter could be isolated, the former were not stable but could be intercepted by MeOH (Scheme 4) or adamantanethione (Scheme 5). The structures of some of the substitution products were established by X-ray crystallography.

The reactions of 3-chloro-3-(chlorosulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (2) with N, O, S, and P nucleophiles occur by substitution of Cl at the S-atom. Whereas, in the cases of secondary amines, alkanols, phenols, thiols, thiophenols, and di- and trialkyl phosphates, the initially formed substitution
products were obtained, the corresponding products with allyl and propargyl alcohols undergo a [2,3]-sigmatropic rearrangement to give allyl and allenyl sulfoxides, respectively. Analogous substitution reactions were observed when 3-chloro-3-(chlorodisulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (3) was treated with N, O, and S nucleophiles. The reaction of 3 with Et3P led to an unexpected product via cleavage of the S S bond (cf. Scheme 13). In the reactions of 2 with primary amines and H2O, the substitution products react further via elimination of HCl to yield the corresponding thiocarbonyl S-imides and the thiocarbonyl S-oxide, respectively. Whereas the latter could be isolated, the former were not stable but could be intercepted by MeOH (Scheme 4) or adamantanethione (Scheme 5). The structures of some of the substitution products were 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:2006
Deposited On:22 May 2012 06:32
Last Modified:05 Apr 2016 15:19
Publisher:Verlag Helvetica Chimica Acta
ISSN:0018-019X
Funders:Swiss National Science Foundation , F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/hlca.200690082
Permanent URL: https://doi.org/10.5167/uzh-54090

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