Efficient one-pot synthesis of N-containing heterocycles by multicomponent coupling of silicon-tethered diynes, nitriles, and isocyanides through intramolecular cyclization of iminoacyl-Zr intermediates.
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.
Zhang
Shaoguang
S
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.
Zhang
Wen-Xiong
WX
Xi
Zhenfeng
Z