Rh(II)-catalyzed intermolecular carboamination of pyridines via double Csp2-H bond activations

We disclose the development of the Rh-catalyzed amine-directed remote 5,6-carboamination protocol of pyridines via dual Csp(2)-H functionalizations. A variety of readily available 2-aminopyridines and 1,2,3-triazoles are allowed for coupling cyclization to access polyfunctionalized azaindoles. Mechanistic studies including DFT calculations unveil that relay carbenoid-electrophilic addition to pyridines and the sequential pyridyl Csp(2)-H amination are involved in this transformation. The post-synthetic utility of this methodology is showcased by versatile and site-selective modification of azaindoles.

Automated summary

The development of a Rh-catalyzed amine-directed remote 5,6-carboamination protocol of pyridines via dual Csp(2)-H functionalizations is disclosed in this study. Various readily available 2-aminopyridines and 1,2,3-triazoles can be coupled and cyclized to access polyfunctionalized azaindoles. Mechanistic studies reveal the involvement of relay carbenoid-electrophilic addition to pyridines and sequential pyridyl Csp(2)-H amination in this transformation. The post-synthetic utility of this methodology is demonstrated through versatile and site-selective modification of azaindoles.