Nickel-catalyzed enantioselective vinylation of aryl 2-azaallyl anions

A unique enantioselective nickel-catalyzed vinylation of 2-azaallyl anions is advanced for the first time. This method affords diverse vinyl aryl methyl amines with high enantioselectivities, which are frequently occurring scaffolds in natural products and medications. This C-H functionalization method can also be extended to the synthesis of enantioenriched 1,3-diamine derivatives by employing suitably elaborated vinyl bromides. Key to the success of this process is the identification of a Ni/chiraphos catalyst system and a less reducing 2-azaallyl anion, all of which favor an anionic vinylation route over a background radical reaction. A telescoped gram scale synthesis and a product derivatization study confirmed the scalability and synthetic potential of this method.

Automated summary

This study introduces a unique enantioselective nickel-catalyzed vinylation method for the synthesis of diverse vinyl aryl methyl amines and enantioenriched 1,3-diamine derivatives, which are frequently found in natural products and medications. The success of this method relies on a Ni/chiraphos catalyst system and a less reducing 2-azaallyl anion, enabling an anionic vinylation route over a background radical reaction. Scalability and synthetic potential of this method are confirmed through a telescoped gram scale synthesis and product derivatization study.