Herein, we report the guanylation of carbodiimides with primary and secondary alkyl/aryl amines and the reduction of CDIs via hydroboration using molecular conjugated bis‐guanidinate (CBG) aluminum alkyl catalysts. The first example of structurally characterized unsymmetrical tetra‐aryl substituted CBG (LH) is reported. The reaction of LH; (L={(Ar1NH)(ArN)−C=N−C=(NAr)(NHAr1)}; Ar1=2,6‐iPr2−C6H3, Ar=2,6‐Me2−C6H3) with AlMe3 solution afforded a LAlMe2 (1) complex. The ligand (LH) and compound 1 were thoroughly characterized, including single‐crystal X‐ray diffraction studies. More importantly, compounds 1 and L'AlMe2 (2); (L’={(ArNH)(ArN)−C=N−C=(NAr)(NHAr)}; Ar=2,6‐Et2−C6H3) are utilized as catalysts for N−H and B−H addition to symmetrical aryl or alkyl carbodiimides to obtain the corresponding guanidines and N‐boryl formamidines in excellent yields. The developed catalytic methods are effectively used for the large‐scale synthesis of guanidine and formamidine derivatives under mild reaction conditions.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.