Post‐Functionalization of Polymers via Orthogonal Ligation Chemistry

Abstract

The establishment of advanced living/controlled polymerization protocols allows for engineering synthetic polymers in a precise fashion. Combining advanced living/controlled polymerization techniques with highly efficient coupling chemistries facilitates quantitative, modular, and orthogonal functionalization of synthetic polymer strands at their chain termini as well as side‐chain functionalization. The review highlights the current status of selected post‐functionalization techniques of polymers via orthogonal ligation chemistries, major characteristics of the specific transformation chemistry, as well as the characterization of the products.

Dynamic Macromolecular Material Design—The Versatility of Cyclodextrin‐Based Host–Guest Chemistry

“…[31] Thec ombination of reversible deactivation radical polymerization and modular ligations is ideal for the generation of polymeric building blocks for dynamic materials. [32] Thec ombination of CDs and synthetic macromolecules based on reversible deactivation radical polymerization and modular ligation methods opens ap lethora of synthetic possibilities and-importantly-several levels of molecular complexity are accessible by the combination of CD hostguest chemistry and polymeric building blocks ( Figure 1). [12a] Taking dynamic hierarchical materials formation as the guiding principle,t he host or guest functional building blocks can be considered as the primary structure that needs to be in place initially.O nt he next hierarchical level, supramolecular complexes formed from functionalized building blocks can be viewed as secondary structures.T he formation of higher order self-assemblies/aggregates of the formed secondary macromolecular structures represents the tertiary structure.T hese levels of complexity can be considered as ah ierarchical system from the molecular via the colloidal levels to the level of dynamic materials.…”

Merging Metallic Catalysts and Sonication: A Periodic Table Overview

“…The Ga(0)/Ag(I) ratio and the virtual Ga(I) loading were decreased to 2:1 and 5 mol %, respectively, under such conditions without loss of activity. An external ligand [18], crown-6, employed to stabilize Ga(I) catalyst, proved to be critical for full conversion. Remarkably, this reaction could be achieved on a gram scale at low catalyst loading (0.1 mol %).…”

“…Late-transition metals, copper in particular, provide a wide range of synthetic applications as Cu(I) species are involved in efficient and expeditious couplings. Click reactions, generally based on copper-catalyzed [3+2]-cycloadditions between azides and alkynes (CuAAC) have met many applications in materials science, as well as macromolecular and biomedicinal chemistries [16][17][18]. Relative to the conventional thermal cycloaddition, which usually yields both 1,4-and 1,5-disubstituted 1,2,3-triazoles, the Cu-catalyzed version is faster and highly regioselective leading to 1,4-regioisomers.…”

Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials

“…6,53,54 The direct synthesis of polyazides requires polymerization of azido monomers at low temperatures, 55,56 and numerous steps involve handling the toxic and potentially explosive azido derivatives. In our case, 2 equiv.…”