Fe/ppm Cu nanoparticles as a recyclable catalyst for click reactions in water at room temperature

Abstract

Nanomicelles housing a terminal alkyne and azide are delivered to ppm Cu-containing nanoparticles that catalyse click reactions in water at rt.

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

“…An alternative that also takes advantage of NP technology has recently appeared, although in this case the catalyst has copper(I) ions on the surface of the nanoparticles rather than within a lipophilic core. These are designated as “Fe/ppm Cu” and are part of the series of new FeCl 3 ‐derived NPs that can be doped with one or more different metals (e.g., Pd, and Pd+Ni) . These particular NPs are made such that each combination of reaction partners (i.e., alkyne+azide) is exposed to 1000 ppm (0.1 mol %) Cu I , which is quite sufficient to fully catalyze the formation of the corresponding triazoles in water at room temperature.…”

“…[67] These and several other fascinating and intriguing discoveries, as detailsa ssociated with the various topics in this review,a re presented herein. There are also many "firsts" in micellar catalysis appliedt oo rganic synthesis, such as:1 )new ligands designed for applications based on micellar catalysis in water; [17,19,23,38] 2) ppm level metal-catalyzed processes; [27,39,50,54,56] 3) new heterogeneous nanoparticles that catalyze av ariety of important, commonly utilized reactions; [27,39,49,50] 4) new hybrid micellar derivatives that incorporate reagents within their structure; [25,49,67,69] 5) industrially important developments on the use of micelles influenced by the presenceo fc o-solvents; [75][76][77][78] and 6) examples of one-pot tandem processes enabled by micellar conditions. [27,81,82,85,88,89] These and several relatede xamples from just the past few years further documentt he potentialo ft his blossoming technology,i llustrating new synthetic chemistry that is sustainable, environmentally responsible, and acknowledges that chemistry as practiced today must be changedt ob ei ns tep with the laws of Nature.…”

“…These are designated as" Fe/ppm Cu" and are part of the series of new FeCl 3 -derived NPs that can be doped with one or more different metals (e.g.,P d, and Pd + Ni). [50] These particular NPs are made such that each combination of reaction partners( i.e.,a lkyne + azide) is exposed to 1000 ppm (0.1 mol %) Cu I ,w hich is quite sufficient to fully catalyze the formation of the correspondingt riazoles in water at room temperature. The preparation of theseN Ps, in general, requireso nly the addition of MeMgClt oF eCl 3 in the presence of the metal of interest( i.e.,i nt his case, CuOAc), all in THF at ambient temperature.…”

Tailor‐Made Polydiacetylene Micelles for the Catalysis of 1,3‐Dipolar Cycloadditions in Water

“…[6] With the aforementioned features in mind and as part of our longstanding interest in the development of catalytic systems, [7] we report here an original formulation of copper salts that were embedded in stable polydiacetylene micelles for the promotion of the [3 + 2] cycloaddition reaction in fully aqueous medium. [8] Micelles are classically made from the self-assembly of amphiphilic molecules in water. [9] At a concentration higher than the critical micelle concentration (CMC), amphiphiles aggregate into spherical structures with a hydrophilic outer layer, interfacing with water, and a central hydrophobic core.…”

“…With the aforementioned features in mind and as part of our longstanding interest in the development of catalytic systems, we report here an original formulation of copper salts that were embedded in stable polydiacetylene micelles for the promotion of the [3+2] cycloaddition reaction in fully aqueous medium …”