Reaction of thiocarbonyl S-methylides with acetylenic dipolarophiles and an unexpected rearrangement of the cycloadducts

被引:0
作者
Gendek, T
Mloston, G
Linden, A
Heimgartner, H
机构
[1] Univ Lodz, Sect Heteroorgan Cpds, PL-90136 Lodz, Poland
[2] Univ Zurich, Inst Organ Chem, CH-8057 Zurich, Switzerland
关键词
D O I
10.1002/1522-2675(200202)85:2<451::AID-HLCA451>3.0.CO;2-9
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The 1,3-dipolar cycloaddition of 2,2,4,4-tetramethyl-3-thioxocyclobutanone S-methylide (2a), generated in situ by thermal extrusion of N-2 from the corresponding 2,5-dihydro-1,3,4-thiadiazole la, with electron-deficient acetylenic compounds yields spirocyclic 2,5-dihydrothiophone derivatives of type 4 (Scheme 2). Mixtures of diastereoisomers are obtained in the case of propiolates. The strained cyclooctyne also undergoes smooth cycloadditions with thioketone S-methylides (Scheme 3). Under acidic conditions, the spirocyclic products of type 4 and 6a isomerize, via opening of the cyclobutanone ring and aromatization of the five-membered ring, to thiophene derivatives of type 7 (Scheme 4).
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页码:451 / 463
页数:13
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