Poly(N-isopropylacrylamide) soluble polymer supports in catalysis and synthesis
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Co- and terpolymers of N-isopropylacrylamide exhibit inverse temperature solubility in water with the polymer's lower critical solution temperature (LCST) being dependent on the polymer's microstructure and the concentration of salt in the water solvent. This solubility behavior has been used to prepare "smart" recoverable homogeneous catalysts and substrates. These catalysts' activity reversibly turns first off and then on as the temperature is first raised and then lowered due to changes in the polymer support's solubility. Such catalysts can be recovered by heating the aqueous solution or by adding brine. Catalysts prepared include both phosphine-ligated transition metal catalysts and acid catalysts. The transition metal catalysts are active in alkene hydrogenation, C-C coupling, and allylic substitution reactions. The acid catalysts are active in acetal hydrolysis. Substrates can be attached to these polymers and their activity likewise can be turned off and on by heating or cooling. Substrate activity on such supports can equal that of a low molecular weight analogue. NMR spectroscopic studies show that a vinyl group bound to PNIPAM has peaks whose line widths in 1H NMR spectroscopy are like those of a low molecular weight compound when a nine-carbon tether chain is used to attach the vinyl group to PNIPAM.