Ultra Rapid Approaches to Mild Macromolecular Conjugation

Abstract

In light of the increasing demand for ultra rapid and mild conjugation chemistries for use in macromolecular chemistry, the present Feature Article provides a critical overview of the very latest developments in this field. The principal aim, therefore, is the provision of a quick selection guide to aid in the formulation of a design strategy for novel functional materials and to provide recommendations for future developments in the chemistries discussed.

Living Radical Polymerization by the RAFT Process – A Third Update

“…Several reviews on combined use of RDRP and 'click chemistry' have appeared. [66][67][68][69][70][71][72] The 'clickable' functionality may be present on the Z or R groups of the RAFT agent (see elsewhere in this review) or in the monomers. These monomers can be incorporated in blocks as a precursor to a polymer brush or copolymerized to provide sites for the attachment of functionality or for crosslinking.…”

“…[38,[66][67][68] The RAFT process can be used to synthesize polymers with clickable moieties at the chain ends through the use of RAFT agents with appropriate functionality on 'Z' or 'R'.…”

“…[62] The process is also given substantial coverage in most recent reviews that, in part, relate to polymer synthesis, living or controlled polymerization or novel architectures. Some of those that include significant mention of RAFT polymerization include reviews on RDRP, [63] mechanism and reagent design, [11,64,65] click chemistry, [66][67][68][69][70][71][72] synthesis of telechelics, [73] the polymerization of carbazole-containing monomers, [74] N-vinyl-1,2,3-triazoles, [75] N-vinyl heterocycles, [76] fluoro-monomers, [77] and glycomonomers, [78][79][80] synthesis of metallopolymers, [81] conjugated block copolymers, [82] dye-functionalized polymers, [83] stimuliresponsive polymers, [84,85] complex architectures, [86,87] polyolefin blocks, [88] biopolymer-polymer conjugates and bioapplications, [59,[89][90][91][92][93] polysaccharide modification, [94,95] polymerization in heterogeneous media, [96,97] microwave-assisted polymerization, [65,98,99] industrial prospects for RDRP, [100,…”

Synthesis of Cyclopentadienyl Capped Polyethylene and Subsequent Block Copolymer Formation Via Hetero Diels‐Alder (HDA) Chemistry

“…[1,2] The conjugation of end-functionalized polymers through orthogonal and efficient coupling reactions (via the click chemistry concept [3] ) is a powerful and widely used tool for the design of various macromolecular architerctures. [4][5][6] In today's polymer chemistry the copper catalyzed azide-alkyne cycloaddition (CuAAC) is the most frequently employed click reaction. [7,8] An alternative efficient coupling method is the hetero Diels-Alder (HDA) reaction between a diene end-functionalized polymer and the electron deficient dithioester end-group of a polymer synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization.…”

Reversible Diels‐Alder Chemistry as a Modular Polymeric Color Switch

“…[ 3 ] Indeed, the modernday chemist has a number of tools available to carry out ultrarapid and mild conjugation chemistry with functionalities such as azide-alkyne, [ 4 ] thiol-ene, [ 5 , 6 ] thiol-isocyanate, [ 7 ] tetrazinealkene, [ 8 ] thio-bromo, [ 9 ] nitrile oxide, [ 10 ] aminooxy-aldehyde/ ketone, [ 11 ] tetrazole-alkene [ 12 ] and dithioester-diene, [ 13 ] to name but a few. [ 14 ] Within this framework of reactions, polymers can be viewed as molecular building blocks providing convenient modular access to complex architectures. Aside from orthogonal and ultrarapid conjugation, signifi cant attention has been drawn to the development of polymeric systems capable of reversibly switching between different physical and/or chemical states in response to external stimuli (e.g.…”