Diversely Substituted Polyamide Structures through Thiol–Ene Polymerization of Renewable Thiolactone Building Blocks

Abstract

A thiolactone derivative of 10-undecenoic acid was used as a renewable AB′ monomer for the one-pot synthesis of diversely substituted polyamide structures, containing amide moieties both in the polymer backbones and in their side chains. Nucleophilic aminolysis of the thiolactone entity liberates a thiol, which further reacts in a stepwise thiol–ene photopolymerization reaction. Using different primary amines, several structurally diverse polyamides, with physical properties dependent on the length and chemical identity of the side chain, were obtained. Postpolymerization oxidation of the sulfide linkages in the polymer backbone to their corresponding sulfoxides and sulfones altered the material, with the degree of oxidation having an impact on the final mechanical properties. Furthermore, this mild and straightforward polymerization procedure was applied for the synthesis of functional polymer networks.

Computational Study and Kinetic Analysis of the Aminolysis of Thiolactones

“…[10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] The biomedical importance of thiolactones is predominantly due to the homocysteinilation of proteins, which is an important risk factor in the study of vascular diseases, such as atherosclerosis. 26 Homocysteinilation occurs when homocysteine thiolactone, a cyclic thioester of the non-protein α-amino acid homocysteine, reacts with the ε-amine group of lysine residues.…”

5‐exo versus 6‐endo Thiyl‐Radical Cyclizations in Organic Synthesis

“…Thiolactones are endocyclic sulfur‐containing analogues of lactones and represent a fascinating class of heterocyclic compounds. Less abundant than lactones, this family of compounds has been identified as having potential impact in numerous fields, including chemical biology, medicinal chemistry, drug discovery, and materials science . Interest in these compounds stems from the unique reactivity bestowed upon them by the incorporation of the sulfur atom, allowing them to undergo chemical, and biochemical reactions not available to lactones.…”

Protected thiol strategies in macromolecular design

“…In a more recent contribution [235], the method was extended to the synthesis of bio-based polyamide structures with varying side-chains. For this purpose, 10-undecenoic acid, a fatty acid derived from castor oil, was transformed in its thiolactone-derivative in a two-step synthesis, giving rise to an amide containing monomer 10-undecenoyl thiolactonamide (Scheme 37).…”