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1,3-dipolare cycloadditionen eines carbonyl-ylids mit 1,3-thiazol-5(4H)-thionen und thioketonen


Meier, Karl-Richard; Linden, Anthony; Mloston, Grzegorz; Heimgartner, Heinz (1997). 1,3-dipolare cycloadditionen eines carbonyl-ylids mit 1,3-thiazol-5(4H)-thionen und thioketonen. Helvetica Chimica Acta, 80:1190-1204.

Abstract

In p-xylene at 150°, 3-phenyloxirane-2,2-dicarbonitrile (4b) and 2-phenyl-3-thia-1-azaspiro[4.4]non-1-ene-4-thione (1a) gave the three 1:1 adducts trans-3a, cis-3a, and 13a in 61, 21, and 3% yield, respectively (Scheme3). The stereoisomers trans-3a and cis-3a are the products of a regioselective 1,3-dipolar cycloaddition of carbonyl-ylide 2b, generated thermally by an electrocyclic ring opening of 4b (Scheme 6), and the C=S group of 1a. Surprisingly, 13a proved not to be a regioisomeric cycloadduct of 1 a and 2b, but an isomer formed via cleavage of the O-C(3) bond of the oxirane 4b. A reaction mechanism rationalizing the formation of 13a is proposed in Scheme 6. Analogous results were obtained from the reaction of 4b and 4,4-dimethyl-2-phenyI-1,3-thiazole-5(4H)-thione (1b, Scheme 3). The thermolysis of 4b in p-xylene at 130” in the presence of adamantanethione (10) led to two isomeric 1:1 adducts 15 and 16 in a ratio of ca. 2: 1, however, in low yield (Scheme 4). Most likely the products are again formed via the two competing reaction mechanisms depicted in Scheme 6. The analogous reactions of 4b with 2,2,4,4-tetramethyIcyclobutane-1,3-thione (11) and 9H-xanthene-9-thione (12) yielded a single 1 :1 adduct in each case (Scheme 5). In the former case, spirocyclic 1,3-oxathiolane 17, the product of the 1,3-dipolar cycloaddition with 2a corresponding to 3a, was isolated in only 11% yield. It is remarkable that no 2:l adduct was formed even in the presence of an excess of 4b. In contrast, 4b and 12 reacted smoothly to give 18 in 81 % yield; no cycloadduct of the carbonyl-ylide 2a could be detected. The structures of cis-3a, 13a, 15, and 18, as well as the structure of 14, which is a derivative of trans-3a, have been established by X-ray crystallography (Figs. 1-3, Table).

Abstract

In p-xylene at 150°, 3-phenyloxirane-2,2-dicarbonitrile (4b) and 2-phenyl-3-thia-1-azaspiro[4.4]non-1-ene-4-thione (1a) gave the three 1:1 adducts trans-3a, cis-3a, and 13a in 61, 21, and 3% yield, respectively (Scheme3). The stereoisomers trans-3a and cis-3a are the products of a regioselective 1,3-dipolar cycloaddition of carbonyl-ylide 2b, generated thermally by an electrocyclic ring opening of 4b (Scheme 6), and the C=S group of 1a. Surprisingly, 13a proved not to be a regioisomeric cycloadduct of 1 a and 2b, but an isomer formed via cleavage of the O-C(3) bond of the oxirane 4b. A reaction mechanism rationalizing the formation of 13a is proposed in Scheme 6. Analogous results were obtained from the reaction of 4b and 4,4-dimethyl-2-phenyI-1,3-thiazole-5(4H)-thione (1b, Scheme 3). The thermolysis of 4b in p-xylene at 130” in the presence of adamantanethione (10) led to two isomeric 1:1 adducts 15 and 16 in a ratio of ca. 2: 1, however, in low yield (Scheme 4). Most likely the products are again formed via the two competing reaction mechanisms depicted in Scheme 6. The analogous reactions of 4b with 2,2,4,4-tetramethyIcyclobutane-1,3-thione (11) and 9H-xanthene-9-thione (12) yielded a single 1 :1 adduct in each case (Scheme 5). In the former case, spirocyclic 1,3-oxathiolane 17, the product of the 1,3-dipolar cycloaddition with 2a corresponding to 3a, was isolated in only 11% yield. It is remarkable that no 2:l adduct was formed even in the presence of an excess of 4b. In contrast, 4b and 12 reacted smoothly to give 18 in 81 % yield; no cycloadduct of the carbonyl-ylide 2a could be detected. The structures of cis-3a, 13a, 15, and 18, as well as the structure of 14, which is a derivative of trans-3a, have been established by X-ray crystallography (Figs. 1-3, Table).

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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:German
Date:1997
Deposited On:18 Nov 2013 09:59
Last Modified:07 Dec 2017 23:46
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche AG, Basel

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