High loading polymer reagents based on polycationic Ultraresins. Polymer-supported reductions and oxidations with increased efficiency

Abstract

Ultraresin 1 was prepared from highly branched polyethylene imine ( M n=10,000) via reductive cross-linking with terephthaldialdehyde. Following quaternization with methyl iodide, the polycationic Ultraresin 2 , with iodide as a counterion, was obtained. These novel resins combine low swelling with high mechanical stability. By anion exchange polycationic Ultraresins carrying borohydride ( 3 ) and periodate ( 22 ) were generated and were investigated as very high loading polymer reagents. Ultra-borohydride resin 3 had a reducing activity of up to 12 mmol/g depending on the substrate. It proved successful in diverse reductions including those of aldehydes, ketones, and nitroolefines. The resin was employed in the reductive amination of aldehydes with an excess of amines, which were removed by the use of a scavenger resin. Periodate resin 22 was obtained with an active loading of up to 5.4 mmol/g and was employed in oxidations of sulfides, diols, hydroquinones, and hydrazines.