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Synthesis of new imidazole 3-Oxides; unexpected deoxygenation of some derivatives in the reaction with 2,2,4,4-Tetramethylcyclobutane-1,3-dithione


Heimgartner, H; Mloston, G; Jasinski, M; Rygielska, D (2011). Synthesis of new imidazole 3-Oxides; unexpected deoxygenation of some derivatives in the reaction with 2,2,4,4-Tetramethylcyclobutane-1,3-dithione. Heterocycles, 83(4):765-776.

Abstract

Whereas the reaction of a series of 1,4,5-trisubstituted imidazole 3-oxides with 2,2,4,4-tetramethylcyclobutane-1,3-dithione gave the corresponding imidazole-2-thiones by a sulfur-transfer reaction via [2+3] cycloaddition, an unexpected deoxygenation occurred in the case of 4-acetyl- 1-(adamantan-1-yl)- 5-methylimidazole 3-oxide. It was shown that the presence of an electron- withdrawing substituent at C(4) and the bulky 1-adamantyl group at N(1) are necessary to enable this reaction course. A reaction mechanism via a zwitterion, followed by a 1,3-cyclization and elimination of an oxathiirane, is proposed.

Whereas the reaction of a series of 1,4,5-trisubstituted imidazole 3-oxides with 2,2,4,4-tetramethylcyclobutane-1,3-dithione gave the corresponding imidazole-2-thiones by a sulfur-transfer reaction via [2+3] cycloaddition, an unexpected deoxygenation occurred in the case of 4-acetyl- 1-(adamantan-1-yl)- 5-methylimidazole 3-oxide. It was shown that the presence of an electron- withdrawing substituent at C(4) and the bulky 1-adamantyl group at N(1) are necessary to enable this reaction course. A reaction mechanism via a zwitterion, followed by a 1,3-cyclization and elimination of an oxathiirane, is proposed.

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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:28 March 2011
Deposited On:28 Mar 2011 14:27
Last Modified:05 Apr 2016 14:53
Publisher:The Japan Institute of Heterocyclic Chemistry
ISSN:0385-5414
Publisher DOI:https://doi.org/10.3987/COM-10-12130
Permanent URL: https://doi.org/10.5167/uzh-47769

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