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Reactions of Ethyl Diazoacetate with Thioketones


Kägi, Martin; Mloston, Grzegorz; Heimgartner, Heinz (1998). Reactions of Ethyl Diazoacetate with Thioketones. Polish Journal of Chemistry, 72(4):678-687.

Abstract

The reaction of diethyl diazoacetate (10) with 9H-fluorene-9-thione (2a), thiobenzophenone (2b), and adamantanethione (2c), respectively, in THF yielded 1,3-dithiolane carboxylates (Scheme 2). Whereas in the first two cases the reaction proceeded at room temperature, heating to 60°C was necessary when the less reactive 2c was used. The additions with 2a and 2c occurred in a regioselective way, yielding 1,3-dithiolane-2-carboxylate 11a and 1,3-dithiolane-4-carboxylate 12c, respectively, with opposite regiochemistry. On the other hand, a mixture of the two regioisomeric cycloadducts 11b and 12b was formed in the case of 2b. The analogous reaction of 10 with the sterically crowded thione 13 gave thiirane 14 as the sole product, and with the corresponding dithione 16, a mixture of the cis- and trans-dithiiranes 17 and 18 was formed (Scheme 3). Desulfurization with tris(dimethylamino)phosphine yielded the alpha,beta-unsaturated esters 15 and 19/20, respectively. The alpha,beta-unsaturated ester 22 was the only product in the reaction of 10 with 9H-xanthene-9-thione (21), which had to be carried out at 60°C.

Abstract

The reaction of diethyl diazoacetate (10) with 9H-fluorene-9-thione (2a), thiobenzophenone (2b), and adamantanethione (2c), respectively, in THF yielded 1,3-dithiolane carboxylates (Scheme 2). Whereas in the first two cases the reaction proceeded at room temperature, heating to 60°C was necessary when the less reactive 2c was used. The additions with 2a and 2c occurred in a regioselective way, yielding 1,3-dithiolane-2-carboxylate 11a and 1,3-dithiolane-4-carboxylate 12c, respectively, with opposite regiochemistry. On the other hand, a mixture of the two regioisomeric cycloadducts 11b and 12b was formed in the case of 2b. The analogous reaction of 10 with the sterically crowded thione 13 gave thiirane 14 as the sole product, and with the corresponding dithione 16, a mixture of the cis- and trans-dithiiranes 17 and 18 was formed (Scheme 3). Desulfurization with tris(dimethylamino)phosphine yielded the alpha,beta-unsaturated esters 15 and 19/20, respectively. The alpha,beta-unsaturated ester 22 was the only product in the reaction of 10 with 9H-xanthene-9-thione (21), which had to be carried out at 60°C.

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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:1998
Deposited On:12 Nov 2013 14:19
Last Modified:18 Apr 2018 11:44
Publisher:Polskie Towarzystwo Chemiczne
ISSN:0137-5083
Funders:Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel, Swiss Federal Commission for Foreign Students
OA Status:Closed
Official URL:http://www.ichf.edu.pl/pjch/pj-1998/pj0498.htm#678
Project Information:
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSwiss National Science Foundation
  • : Funder
  • : Grant ID
  • : Project TitleF. Hoffmann-La Roche AG, Basel
  • : Funder
  • : Grant ID
  • : Project TitleSwiss Federal Commission for Foreign Students

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