Synthesis of a pyridine substituted polycarbodiimide and its use as a solid support for chemical reagents

Optically active, polycarbodiimides 3(a, b & c) with pyridine pendant groups were synthesized using [(R) - 2,2'- binaphthoxy] (di-isopropoxy) titanium(IV) catalyst. The polymers were characterized by H-1 and C-13 NMR, and IR. Thermal stability of these polymers (up to 162 degrees C by TGA), allows thermally demanding chemical transformations on their side chains without decomposition. Advantages include fine-tunability of the other pendant group of the carbodiimide monomer. This allows one to optimize the properties of the polymer without undergoing copolymerization or further post-polymerization modifications. Borane (BH3) was coordinated to poly 3 (a & b) to prepare the functional polymers 4 (a & b) respectively. A strong IR signature peak at 2368 cm(-1) supports BH3 coordination. Gravimetric analysis indicates 97-99% borane complexation of the pyridine units. In addition, the thermal stability increased to 194 degrees C in poly 4a is consistent with the incorporation of BH3 to the pendant pyridine of the helical polycarbodiimide 3a. Poly 4 (a & b) can be used as supported reagents and successfully reduced the carbonyl compounds (5 a-e) in moderate to excellent yields (60-100%) and are shown to be efficient, non-volatile, stable, and mild supported-reducing reagents. Upon completion of the reduction reaction, the polymer support was quantitatively recycled as required for a green solid catalyst support. (C) 2010 Elsevier Ltd. All rights reserved.