Hydrogen-bonding organocatalysts for ring-opening polymerization

Abstract

In the ring-opening polymerization (ROP) of cyclic esters and carbonates, hydrogen-bonding organocatalysis offers an interesting alternative to metal-based and enzymatic catalysis to access biocompatible and biodegradable polymers. The design of catalysts, strategies of activation and mechanistic elucidations are highlighted. Recent developments with functionalized monomers for applications in nanomaterials and biomedicine have opened perspectives to broaden the scope of future catalytic systems. In the field of sustainable chemistry, hydrogen-bonding structures devoted to ROP have become a full-fledged class of catalysts.

Structural and Mechanistic Insights into s‐Block Bimetallic Catalysis: Sodium Magnesiate‐Catalyzed Guanylation of Amines

“…[10] Furthermore, they find extensive applications as precursors of ancillary ligands forn umerous transition-,l anthanoid-, and main-group-metal complexes [11] and they can also be employed as organocatalysts. [12] Atom-economical catalytic addition of aminestocarbodiimides (guanylation reaction, Scheme 1) constitutes one of the most straightforwardr outes to accessN -substituted guanidines. [9] Althoughc ertain guanylationsc an be accomplished catalystfree, thesep rocesses have high kinetic barriers that require the use of harsh reaction conditions, which restricts their application to activated primary aliphatic amines.…”

Rate Accelerated Organocatalytic Ring-Opening Polymerization of l-Lactide via the Application of a Bis(thiourea) H-bond Donating Cocatalyst

“…2–5 This class of compounds features a wide array of functional motifs and geometries and has been employed in a multitude of reactions including Henry reactions, hydroaminations, conjugate additions and ring-opening polymerization (ROP). 6–12 While the wealth of chemistry offered by H-bonding catalysts has attracted numerous research groups, these systems can require high catalyst loadings and/or long reaction times.…”

Organocatalysts for the Synthesis of Poly(ethylene terephthalate‐co‐isosorbide terephthalate): A Combined Experimental and DFT Study

“…Organocatalysis for polymerization reactions is a field that has gained a huge interest these last 15–20 years, notably in a sustainable chemistry background . Most of the studies were devoted to chain growth reactions, especially the ring‐opening polymerization of various types of heterocycles and the polymerization of acrylic and methacrylic monomers.…”