Organocatalysis of CN/CN and CC/CN Exchange in Dynamic Covalent Chemistry

The reversibly formed CN bond plays a very important role in dynamic covalent chemistry and the CN/CN exchange of components between different imine constituents to create dynamic covalent libraries has been extensively used. To facilitate diversity generation, we have investigated an organocatalyzed approach, using L ‐proline as catalyst, to accelerate the formation of dynamic libraries of [ n × n ] imine components. The organocatalysis methodology has also been extended, under somewhat modified conditions, to reversible CC/CN exchange processes between Knoevenagel derivatives of barbituric acid and imines, allowing for the generation of increased diversity.