Marrying click chemistry with polymerization: expanding the scope of polymeric materials

Abstract

Click chemistry constitutes a class of reactions broadly characterized by efficiency, selectivity, and tolerance to a variety of solvents and functional groups. By far the most widely utilized of these efficient transformation reactions is the Cu(I)-catalyzed azide-alkyne cycloaddition. This reaction has been creatively employed to facilitate the preparation of complex macromolecules, such as multiblock copolymers, shell or core cross-linked micelles, and dendrimers. This critical review highlights the application of click chemistry, in particular the Cu(I)-catalyzed azide-alkyne cycloaddition, to the synthesis of a wide variety of new materials with possible uses as drug delivery agents, tissue engineering scaffolds, and dispersible nanomaterials (83 references).

Metal-catalyzed azide-alkyne “click” reactions: Mechanistic overview and recent trends

“…The only drawback is the need of large quantities of this catalyst mixture that is slow. Indeed, various nitrogen ligands accelerate the Cu(I) catalysis of the "click" reaction and allow using 1% or a few % Cu (I) catalyst [20,26]. Recently we reported that using a recyclable dendritic nanoreactor in water only, it was possible to decrease the Cu(I) amount using the CuSO 4 •5H 2 O + sodium ascorbate catalyst to 1 ppm or only a few ppm with various applications to biomedical targets [27a].…”

“…The concept of "click chemistry" proposed by Kolb, Finn and Sharpless in 2001 [1] has revolutionized molecular engineering including applications to organic and medicinal chemistry [2][3][4][5][6][7][8][9][10][11], polymer science and materials science [12][13][14][15][16][17][18][19][20][21]. Among the various "click" reactions responding to the requirements of this concept, the most generally used one is the copper(I)-catalyzed reaction between terminal alkynes and azides (CuAAC) selectively yielding 1,4-disubstituted 1,2,3-triazoles, that was reported independently by the Sharpless-Fokin [22] and the Meldal groups in 2002 [ 23,24].…”

Intramolecular Cross-linking of Polymers Using Difunctional Acetylenes via Click Chemistry

“…Click reactions have been widely used for the synthesis of polymers with different compositions and topologies, ranging from linear (telechelic [29], macromonomer [30,31], macrophotoinitiator [32,33] and block co-polymer [34][35][36]) to nonlinear macromolecular structures (graft [37][38][39], star [40,41], miktoarm star [42,43], H-type [44], dendrimer [45][46][47], dendronized linear polymers [48,49], macrocyclic polymers [50,51], self-curable polymers [52][53][54], network systems [55,56] and polymeric nanoparticles [14,57]). Recently, the development and application of click chemistry in polymer and material science has been extensively reviewed [58][59][60][61][62][63].…”

In-vitro cytotoxic activities of poly(2-ethyl-2-oxazoline)-based amphiphilic block copolymers prepared by CuAAC click chemistry

“…And then, many groups have extensively used this 'click' reaction to synthesize a wide variety of block copolymers (such as AB, ABC, ABA, (AB) n , etc.) [16][17][18][19][20][21][22]. To take advantage of this efficient strategy, recently, the poly(2-alkyl-2-oxazoline)-based amphiphilic block copolymers can be simply prepared by combination of coordination-insertion ROP (ring opening polymerization) and living CROP (cationic ring opening polymerization) with CuAAC click reactions [23,24].…”