Insertion of acyl cyanides into azazirconacydopentenes derived from 1,3-azadienes has been described, which affords acyl- or non-acyl-substituted pyrroles upon acidic quenching. These reactions are initialized through C=O insertion into the azazirconacycle to afford seven-membered oxaazazirconacycles. In the cases of 1,4- or 1,2,4-substituted azadienes, addition of a second molecule of acyl cyanide followed by cyclization upon acidic quenching leads to acyl-substituted pyrroles. In the cases of 1,3,4-substituted azadienes, the addition of a second molecule of acyl cyanide cannot proceed due to the steric hindrance caused by the R-3 group on the zirconium intermediate. Acidic quenching of the resulting zirconium intermediate affords non-acyl-substituted pyrroles.
Xiong MJ,Yu SS,Jie X,et al. Reactions of Zirconocene-1-Aza-1,3-diene Complexes with Acyl Cyanides: Substrate-Dependent Synthesis of Acyl- or Non-Acyl-Substituted Pyrroles[J]. Organometallics,2015,34(23):5597-5601.