Molecularly Imprinted Nanoreactors for Regioselective Huisgen 1,3-Dipolar Cycloaddition Reaction

Abstract

A molecularly imprinted polymer has been successfully utilized as nanoreactors for Huisgen 1,3-dipolar cycloaddition of azides and alkynes, leading to high product regioselectivity and kinetic acceleration. The MIP nanoreactors also showed remarkable selectivity toward the reactant structures, so that the "best fit" product was mostly amplified during the reaction. In contrast to previously reported regioselective MIPs, the present imprinted cavities bind reactants by means of only noncovalent molecular interactions, the same as that normally involved in biological systems. The results support the concept of drug "cloning" that further extends both the anti-idiotypic imprinting and in-cavity synthesis approaches into the modern drug discovery area.

‘Click’ Chemistry in Polymer and Materials Science

“…[55] Catalytic effects with respect to the regioselectivity of the cycloaddition reaction were observed.…”

pH‐Sensitive Water‐Soluble Nanospheric Imprinted Hydrogels Prepared as Horseradish Peroxidase Mimetic Enzymes

“…[2][3][4] Molecularly imprinted polymers (MIPs) have been successfully employed to generate catalytically active binding sites for the mimicking of a myriad of enzymes. [5][6][7] With transition-state analogues (TSAs) as the templates, highly crosslinked, soluble, imprinted microgel catalysts and soluble imprinted nanogels with a single cavity per particle for carbonate hydrolysis have been reported by Resmini [8,9] and Wulff, respectively. [10,11] In these homogeneous phase models, mass transfer was significantly facilitated in contrast to the traditional insoluble imprinted polymers, though the catalytic activity is still modest in aqueous media.…”

Preparation and Catalytic Performances of a Molecularly Imprinted Ru‐Complex Catalyst with an NH2 Binding Site on a SiO2 Surface

“…[83][84][85] Ye et al prepared molecularly imprinted nanoreactors containing -COOH binding sites for regioselective 1,3-dipolar cycloaddition reactions. [80] Wulff et al designed a molecularly imprinted cavity, the shape of which matched that of a transition state of basic ester hydrolysis, with two N,N'-diethyl-A C H T U N G T R E N N U N G amidine groups as binding sites. [86,87] Such organic functional groups spatially arranged on the walls of molecularly imprinted cavities have the potential to be applied as molecular binding sites for selective catalyses.…”