A Chromium Catalytic System for the Synthesis of Aryl‐Substituted 1,3,5‐Triazines and Pyrimidines by Acceptorless Dehydrogenative Coupling

Abstract A novel and highly efficient method for the synthesis of 2,4,6‐triaryl‐1,3,5‐triazines and 2,4,6‐trisubstituted pyrimidines from amidines and alcohols has been established. Using an Earth‐abundant and air‐stable chromium salt catalyst and a phosphine‐free ligand, the developed Cr‐catalyzed acceptorless dehydrogenative coupling provides 1,3,5‐triazines and pyrimidines with high yields and good functional group tolerance. Moreover, the synthetic value of this operationally simple protocol was demonstrated by gram‐scale experiment and the synthesis of the linker to construct various supramolecular complexes.