Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex
Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex
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通过 1,2-乙烯二硫醇铑配合物进行的铑催化 1,4-二硫英异构化和炔烃交换反应
DOI：
10.1021/acs.organomet.8b00498
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发表时间：
2018
期刊：
影响因子：
2.8
通讯作者：
and Masahiko Yamaguchi*
中科院分区：
文献类型：
--
作者：
Mieko Arisawa*;Kyosuke Sawahata;Takuya Ichikawa;and Masahiko Yamaguchi*
铑催化的1，4-二噻烯的异构化和炔交换反应通过两个C-S键的断裂发生。2，5-和2，6-二取代的1，4-二噻英在110 ℃下在甲苯中进行异构化反应，得到异构体的平衡混合物。在150 °C下，1，4-二噻英与乙炔二甲酸二甲酯反应得到不对称的2，3-二（甲氧羰基）-1，4-二噻英和2，3-二（甲氧羰基）噻吩，后者是由1，4-二噻英脱硫形成的。炔与1，2-二硫杂环丁烷的相关反应得到2，3-二（甲氧羰基）噻吩。这些反应被认为涉及1，2-乙烯二硫醇合铑中间体。
Rhodium-catalyzed isomerization and alkyne exchange reactions of 1,4-dithiines occurred by cleavage of two C–S bonds. The 2,5- and 2,6-disubstituted 1,4-dithiins underwent isomerization reactions in toluene at 110 °C, providing equilibrium mixtures of isomers. At 150 °C, the reaction of 1,4-dithiins and dimethyl acetylenedicarboxylate gave unsymmetric 2,3-di(methoxycarbonyl)-1,4-dithiins and 2,3-di(methoxycarbonyl)thiophenes, the latter of which were formed by desulfurization of the 1,4-dithiins. A related reaction of the alkyne and a 1,2-dithiete gave a 2,3-di(methoxycarbonyl)thiophene. These reactions are considered to involve 1,2-ethenedithiolato rhodium intermediates.