Metal-free synthesis of highly substituted 2-aminopyridines by formal [3+3] annulation of α,α-dicyanoalkenes with imines

-cyanoimines is reported. This strategy provides a straightforward and efficient route for the construction of highly substituted 2-aminopyridines with good yields and high chemoselectivity. The practical synthetic utility of this methodology is demonstrated by structural diversification of the products and further derivatization into bioactive molecules.