“…Yin and Gao also reported that the metallocenes of Ti(IV) [16] and Zr(IV) [17] were highly efficient Lewis acids for other carbonyl-transformation reactions. In recent years, HfCl 4 , another closely related Group IVB transition metal salt, was revealed to possess even superior activities in many metal Lewis acid-catalyzed reactions [18][19][20], especially those involving carbonyl activation [21][22][23][24]. In addition, it is noteworthy that ZrOCl 2 ·8H 2 O, ZrCl 4 , and HfCl 4 showed high catalytic activity in the synthesis of 2-substituted benzimidazoles from o-phenylenediamines and orthoesters [25].…”