Multicomponent Reactions and Multicomponent Cascade Reactions for the Synthesis of Sequence‐Controlled Polymers

Abstract

Control over the monomer sequence during polymerization has attracted great attention in polymer science, but it remains a serious challenge. Recently, multicomponent reactions have been playing a significant role in the synthesis of sequence-controlled polymers due to their inherent advantage of combining three or more starting materials in time-saving, one-pot operations to afford complex microstructures. In this feature article, the recent representative developments in the synthesis of sequence-controlled polymers by multicomponent reactions are highlighted to give insight on the design of novel sequence-controlled polymers with sufficient molecular diversity and complexity. The main part of this article is divided into three sections according to the different polymerization strategies using multicomponent reactions: direct multicomponent polymerization, multicomponent cascade polymerization, and iterative multicomponent reaction, respectively. It is anticipated that this feature article may provide some guidance for the fabrication of sequence-controlled polymers by multicomponent reactions.

Selectivity in multiple multicomponent reactions: types and synthetic applications

“…There are, however, cases where this indiscriminate reactivity is synthetically useful: MCR polymerizations, typically involving two doubly functionalized reactants, which yield macromolecular adducts [9–11]. In these processes, the reactivity of the equivalent FGs is nearly identical in the reactants and in the oligo/polymeric intermediates, as they are usually connected through long linear alkyl chains.…”

A New Strategy to Synthesize α,ω‐Dihydroxy Multiblock Copolymers via [CpRu(CH3CN)3]PF6/Quinaldic Acid Catalyst

“…Multiblock copolymers (MBCs) containing random (ABBAAB) and alternating (ABABAB) segments have attracted significant scientific interest, owing to their resulting microphase‐separated morphologies, different thermal and mechanical properties with a growing list of realized and potential applications . Currently, major sy nthesis methods to get MBCs relying on polycondensation can be divided into two categories, that is, click chemistry and coupling chemistry of α,ω‐dihydroxy to form urethane, ester, or amide bonds . Although some of the MBCs have been successfully prepared and got some applications, those MBCs were mainly focused on thermoplastic materials with superior performance .…”

“…[1][2][3][4][5] Currently, major synthesis methods to get MBCs relying on polycondensation can be divided into two categories, that is, click chemistry and coupling chemistry of α,ω-dihydroxy to form urethane, ester, or amide bonds. [6][7][8][9][10][11][12] Although some of the MBCs have been successfully prepared and got some applications, those MBCs were mainly focused on thermoplastic materials with superior performance. [13][14][15][16][17][18][19][20][21][22] Therefore, having a special terminal groups of MBCs which can be used as thermosetting material were not yet received much attention and research.…”

Direct comparison of solution and solid phase synthesis of sequence-defined macromolecules

“…Whilst many different approaches exist, the use of multi-component reactions seems to be a logical choice within this area and such reactions have indeed been shown to be highly effective tools for the synthesis of sequence-defined macromolecules. 17,18,[33][34][35][36][37][38][39][40] In particular, the Passerini three-component reaction (P-3CR, Scheme 1, top left) between an acid, an aldehyde and an isocyanide, first discovered in 1921, 41 has been reported to be a highly effective technique in sequence-defined oligomer synthesis. [33][34][35][36] On the other hand, "click" chemistry, a term first introduced by Sharpless and coworkers in 2001, 42 is also an ideal concept for sequence-defined synthesis.…”