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Synthesis of Imidazopyridinium-Fused Metallacycloallene via One-Pot Reaction of η2-Alkynol-Coordinated Osmacycle with 2-Aminopyridine
Organometallics ( IF 2.8 ) Pub Date : 2017-11-01 00:00:00 , DOI: 10.1021/acs.organomet.7b00629
Lipeng Long 1 , Xiaoxi Zhou 1 , Tongdao Wang 1 , Zhixin Chen 1 , Hong Zhang 1 , Haiping Xia 1
Affiliation  

Metallacycloallenes are metallacyclic derivatives of cyclic allenes, in which a CH2 (type A) or CH (type B) segment is formally replaced by an isolobal transition-metal fragment. In constrast to the well-developed chemistry of metallacycloallenes of type A, the synthesis of metallacycloallenes with the structural features of type B has met with limited success. In this study, we present the reaction of η2-alkynol-coordinated osmacycle 1 with 2-aminopyridine in the presence of hypervalent iodine reagent, leading to the formation of imidazopyridinium-fused 4-osmacyclohexa-2,3,5-trienone 2 and 4-osmacyclohexa-2,5-dienone 3. Two key intermediates, η2-ethynyl ketone coordinated osmacycle 4 and 4-osmacyclohexa-2,5-dienone 5, were isolated and fully characterized, which suggest the hypervalent iodine reagent plays an important role in the formation of the fused metallacycloallene 2.

中文翻译:

通过η的一锅反应Imidazopyridinium稠合Metallacycloallene的合成2炔醇配位Osmacycle与2-氨基吡啶

金属环戊烯是环状烯的金属环衍生物,其中CH 2A型)或CH(B型)链段被异族过渡金属片段形式取代。与发达的A型金属环烯化合物化学相反,具有B型结构特征的金属环烯化合物的合成取得了有限的成功。在这项研究中,我们提出的反应η 2炔醇协调osmacycle 1与高价碘试剂存在下2-氨基吡啶,从而导致imidazopyridinium稠合4- osmacyclohexa -2,3,5- trienone的形成2和4-osmacyclohexa-2,5-二烯酮3。两个关键中间体,η 2 -乙炔基酮协调osmacycle 4和4- osmacyclohexa己-2,5-二烯酮5,分离并充分表征,这表明所述高价碘试剂起着熔融metallacycloallene的形成中起重要作用2
更新日期:2017-11-02
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