Deprotonative metalation of chlorothiophene with Grignard reagent and catalytic cis-2, 6-dimethylpiperidine under mild conditions
Deprotonative metalation of chlorothiophene with Grignard reagent and catalytic cis-2, 6-dimethylpiperidine under mild conditions
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温和条件下格氏试剂和催化顺式 2, 6-二甲基哌啶对氯噻吩的去质子金属化
DOI：
10.1055/s-0033-1338385
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发表时间：
2013
期刊：
影响因子：
2
通讯作者：
Atsunori Mori
中科院分区：
文献类型：
--
作者：
Shunsuke Tamba. Kenji Ide;Keisuke Shono;Atsushi Sugie;Atsunori Mori
在室温下，用催化量的顺式-2，6-二甲基哌啶（cis-2，6-dimethylpiperidine，C2 H4）和烷基格氏试剂使氯代噻吩发生去质子化金属化反应3小时，得到相应的噻吩基格氏试剂。在带有N-杂环卡宾（NHC）配体的镍催化剂存在下，用由此金属化的氯噻吩进行导致头-尾型聚（3-取代噻吩）的聚合。钯催化的与芳基溴的交叉偶联反应也以良好至优异的产率得到芳基化噻吩，同时C-Cl键保持完整。
Deprotonative metalation of chlorothiophene takes place with a catalytic amount ofcis-2,6-dimethylpiperidine (DMP) and an alkyl Grignard reagent at room temperature for three hours to give the corresponding thienyl Grignard reagent. Polymerization leading to head-to-tail-type poly(3-substituted thiophene) with the thus metalated chlorothiophene proceeds in the presence of a nickel catalyst bearing anN-heterocyclic carbene (NHC) ligand. Palladium-catalyzed cross-coupling reaction with aryl bromides also gives arylated thiophenes in good to excellent yields while the C–Cl bond remains intact.