Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Chemistry. 2010 Jul 26;16(28):8419-26. doi: 10.1002/chem.201000708.
An efficient multicomponent synthesis of 5-azaindoles and dihydropyrrolo[3,2-c]azepines was achieved by zirconocene-mediated coupling of silicon-tethered diynes, nitriles, and isocyanides. The synthesis, structures, and intramolecular cyclization of mono- and bis(iminoacyl)--Zr intermediates were investigated to elucidate the reaction process. Upon hydrolysis, the isolated mono(iminoacyl)--Zr intermediates underwent intramolecular cyclization to afford tetrasubstituted 5-azaindoles, whereas intramolecular cyclization of bis(iminoacyl)--Zr intermediates led to the formation of dihydropyrrolo[3,2-c]azepines. The structure of a bis(iminoacyl)--Zr intermediate, formed through insertion of two molecules of CyNC into the Zr--C bond, and structures of two dihydropyrrolo[3,2-c]azepines were characterized by single-crystal X-ray structural analysis.
通过锆介导的硅桥联二炔、腈和异氰化物的偶联，实现了 5-氮杂吲哚和二氢吡咯并[3,2-c]氮杂环庚烷的高效多组分合成。研究了单-和双（亚氨基甲酰基）-Zr 中间体的合成、结构和分子内环化，以阐明反应过程。水解后，分离得到的单（亚氨基甲酰基）-Zr 中间体发生分子内环化，得到四取代的 5-氮杂吲哚，而双（亚氨基甲酰基）-Zr 中间体的分子内环化则生成二氢吡咯并[3,2-c]氮杂环庚烷。通过两个 CyNC 分子插入 Zr-C 键形成的双（亚氨基甲酰基）-Zr 中间体的结构以及两个二氢吡咯并[3,2-c]氮杂环庚烷的结构通过单晶 X 射线结构分析进行了表征。
