Macromolecular Engineering through Click Chemistry and Other Efficient Transformations

Abstract

Precision synthesis of advanced polymeric materials requires efficient, robust, and facile chemical reactions. Paradoxically, the synthesis of increasingly intricate macromolecular structures generally benefits from exploitation of the simplest reactions available. This idea, combined with requirements of high efficiency, orthogonality, and simplified purification procedures, has led to the rapid adoption of “click chemistry” strategies in the field of macromolecular engineering. This Perspective provides context as to why these newly developed or recently reinvigorated reactions have been so readily embraced for the preparation of polymers with advanced macromolecular topologies, increased functionality, and unique properties. By highlighting important examples that rely on click chemistry techniques, including copper(I)-catalyzed and strain-promoted azide−alkyne cycloadditions, Diels−Alder cycloadditions, and thiol−ene reactions, among others, we hope to provide a succinct overview of the current state of the art and future impact these strategies will have on polymer chemistry and macromolecular engineering.

Ruthenium-Catalyzed Azide Alkyne Cycloaddition Reaction: Scope, Mechanism, and Applications

“…4 The report from Scripps, meanwhile, provides a procedure for the reaction in solution, employing convenient in situ reduction of copper(II) sulfate with ascorbic acid to form the necessary Cu(I) species. 5 This Cu-catalyzed azide alkyne cycloaddition (CuAAC) has since been applied to a great extent, [9][10][11][34][35] not only in chemistry but also in related areas such as biology [36][37][38] and new materials, 39 mainly due to the experimental simplicity of the reaction, as well as its robustness and the high yields obtained. The reaction is tolerant to almost every functional group, can be performed in a wide range of solvents, including water, and has a very favorable atom economy 40 as all ingoing components are, at least in theory, incorporated into the product.…”

Photoinitiated Polymerization: Advances, Challenges, and Opportunities

“…46,47 These reactions were also utilized as environmentally friendly "click" coupling processes in various synthetic applications, since in contrast to the other methods, they usually proceed in the absence of solvent under benign reaction conditions without the use of any potentially toxic metal. [48][49][50][51] For many curing applications fully formulated mixtures, which contain all initiators monomers and additives, are supplied to customers. However, such formulations may not exhibit a good shelf life due to the initiation on storage.…”

High-performance triazole-containing brush polymers via azide–alkyne click chemistry: a new functional polymer platform for electrical memory devices

“…The crude product was dissolved in CHCl 3 (150 ml) and washed with brine (50 ml) three times. The organic layers were then dried over magnesium sulfate (MgSO 4 Figure S1a).…”

“…[2][3][4][5][6] In particular, Cu(I)-catalyzed azide-alkyne cycloaddition has been well established as a representative click chemistry reaction capable of selectively combining two components via covalent bonds in excellent yields. [1][2][3][4][5][6][7] This click reaction, however, has some drawbacks, such as the requirement of a metal-based catalyst for achieving a high reaction conversion and controlling regioselectivity, the explosive nature of some azide substances and the negative effects of the formed triazole ring on solubility and other properties such as electronic and optoelectronic properties. 8 Extensive effort has been devoted to overcome such drawbacks, resulting in the development of metal-free azide-alkyne click chemistry as well as azide-free click chemistry.…”