Unsymmetrical salen-type ligands: High yield synthesis of salen-type Schiff bases containing two different benzaldehyde moieties

Salen-type Schiff base ligands incorporating two different benzylidene moieties and a diamine backbone were synthesized in high yield (80-90%) under mild conditions via a stepwise approach. In the first step, anhydrous hydrochloric acid was used to selectively protect one amino group of the vicinal diamine backbone. The resulting ammonium salt was added to a substituted benzaldehyde providing access to a mono-imine product. This compound reacted with an equivalent of a different benzaldehyde in the presence of triethylamine to afford an unsymmetrical salen-type ligand. This synthetic method allows facile access to a plethora of salen-type Schiff base ligands with easily tunable steric and electronic properties.