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Regioselektive 1,3-Dipolare Cycloadditionen eines ‘Thiocarbonyl-methanids’ ((Alkylidensulfonio)methanids) mit aromatischen Sulfinen


Mloston, Grzegorz; Linden, Anthony; Heimgartner, Heinz (1996). Regioselektive 1,3-Dipolare Cycloadditionen eines ‘Thiocarbonyl-methanids’ ((Alkylidensulfonio)methanids) mit aromatischen Sulfinen. Helvetica Chimica Acta, 79(1):31-40.

Abstract

Reaction of the spirocyclic 2,5-dihydro-l,3,4-thiadiazole 7 and thiobenzophenone S-oxide (6a) in THF at 45° yielded the spirocyclic 1,3-dithiolane 1-oxide 8, thiirane 9, and the diazane derivative 10 in a ratio of 61:15:23 (Scheme 2). The formation of 8 is rationalized by a 1,3-dipolar cycloaddition of ‘thiocarbonyl-methanide’ 1, generated from 7 by thermal elimination of N2, and the C=S bond of sulfine 6a. Cyclization of intermediate 1 leads to thiirane 9. Under the same conditions, 7 and adamantane-2-thione S-oxide (6b) or 2,2,4,4-tetramethyl-3-thioxocyclobutanone S-oxide (4) reacted to give only 9 and 10 but no cycloadduct of type 8 (Scheme 4 ). With the aim to favor the formation of 8, a mixture of 6a and 1.1 equiv. of 7 was heated to 45° without any solvent in a sealed tube. The ratio of products was only slightly different from that of the thermolysis in THF. An analogous experiment with 7 and 9H-fluorene-9-thione S-oxide (6c) yielded cycloadduct 13 and 9 (Scheme 5 ). It is most interesting that the 1,3-dipolar cycloadditions of 1 and the sulfines 6a and 6c proceeded with different regioselectivity. A reaction mechanism for the unexpected formation of 10 is proposed in Scheme 7. The key step is the base-catalyzed ring opening of 7 and the nucleophilic addition of the thereby formed thiolate 21 onto the sulfonium ion 19

Reaction of the spirocyclic 2,5-dihydro-l,3,4-thiadiazole 7 and thiobenzophenone S-oxide (6a) in THF at 45° yielded the spirocyclic 1,3-dithiolane 1-oxide 8, thiirane 9, and the diazane derivative 10 in a ratio of 61:15:23 (Scheme 2). The formation of 8 is rationalized by a 1,3-dipolar cycloaddition of ‘thiocarbonyl-methanide’ 1, generated from 7 by thermal elimination of N2, and the C=S bond of sulfine 6a. Cyclization of intermediate 1 leads to thiirane 9. Under the same conditions, 7 and adamantane-2-thione S-oxide (6b) or 2,2,4,4-tetramethyl-3-thioxocyclobutanone S-oxide (4) reacted to give only 9 and 10 but no cycloadduct of type 8 (Scheme 4 ). With the aim to favor the formation of 8, a mixture of 6a and 1.1 equiv. of 7 was heated to 45° without any solvent in a sealed tube. The ratio of products was only slightly different from that of the thermolysis in THF. An analogous experiment with 7 and 9H-fluorene-9-thione S-oxide (6c) yielded cycloadduct 13 and 9 (Scheme 5 ). It is most interesting that the 1,3-dipolar cycloadditions of 1 and the sulfines 6a and 6c proceeded with different regioselectivity. A reaction mechanism for the unexpected formation of 10 is proposed in Scheme 7. The key step is the base-catalyzed ring opening of 7 and the nucleophilic addition of the thereby formed thiolate 21 onto the sulfonium ion 19

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Additional indexing

Other titles:Regioselective 1,3-Dipolar Cycloadditions of a ‘Thiocarbonyl-methanide’ ((Alkylidenesulfonio)methanide) with Aromatic Sulfines
Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:German
Date:1996
Deposited On:25 Nov 2013 08:30
Last Modified:05 Apr 2016 17:11
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Polnisches Nationalkomitee zur Förderung der wissenschaftlichen Forschung, Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/hlca.19960790105
Permanent URL: https://doi.org/10.5167/uzh-85430

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