Click chemistry strategies for the accelerated synthesis of functional macromolecules

Abstract

Click chemistry is one of the most powerful strategies for constructing polymeric soft materials with precise control over architecture and functionality. In this review, we provide a comprehensive summary of the state-of-the art for synthesizing functional polymers and their expanding range of applications. The synthetic and mechanistic aspects are discussed for key reactions that fulfill "click" requirements and their applications in construction of macromolecules with linear, branched, and other complex architectures are described.

Diels–Alder Cycloadditions of Bio-Derived Furans with Maleimides as a Sustainable «Click» Approach towards Molecular, Macromolecular and Hybrid Systems

“…The nature of the substituents at the furan ring and N-atom of maleimide have a significant influence on the efficiency and selectivity of cycloaddition. In some cases, HMF-derived furans showed higher endo-selectivity in DA reactions with maleimides than furfural-derived furans (Table 1, entries [4][5][6][7][8][11][12][13]. N-Aryl maleimides typically showed lower diastereoselectivity in cycloadditions with furans than N-alkyl maleimides.…”

“…The major synthetic transformations of renewable furans are focused on the production of biofuels, chemicals and materials, in accordance with the sustainability concept [6][7][8][9][10][11]. Diels-Alder (DA) cycloaddition represents an important type of dynamic process that has found wide applications as a "click" reaction for the production of monomolecular products as well as for materials development [12][13][14]. The common mechanism of DA reactions includes the interaction of the highest occupied molecular orbital (HOMO) of the diene with the lowest unoccupied molecular orbital (LUMO) of dienophile, resulting in the formation of a new, six-membered ring.…”

New Opportunity: Machine Learning for Polymer Materials Design and Discovery

“…Some cutting-edge techniques, such as click polymerizations, chain-shuttling reactions, and controlled living radical polymerizations, have been successfully put into use for the design of new polymers meeting the market requirements. [26][27][28][29] Most methods of polymers design remain in the modification of repeating unit to meet the requirements, including graft polymerization, ionized gas treatment, and wet chemical method. [30][31][32][33] Presently, especially in the era of big data, the data volume of polymer materials is increasing with the rapid development of experimental characterization and data storage technology.…”

RAFT-Based Polymers for Click Reactions

“…Therefore, the design of a synthetic route is crucial to produce macromolecules with the desired architecture and functionalities. Since the 2000s, the numerous publications and reviews summarized the application of click reactions in the synthesis of macromolecules with complex architecture [ 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 ]. Nowadays, click reactions are used to assemble macromolecules, the parts of which are pre-prepared by living anionic polymerization, pseudo-living cationic polymerization, and reversible deactivation radical polymerization (RDRP) [ 39 ].…”