The mechanistic duality of (thio)urea organocatalysts for ring-opening polymerization
Date of Original Version
Among the various catalysts for ROP, H-bonding organocatalysts stand out in the precise level of reaction control they are able to render during ROP. The H-bonding class of organocatalysts are thought to effect ROP via dual activation of both monomer and chain end. (Thio)urea mediated ROP has experienced a renaissance as a new polymerization mechanism-mediated by imidate or thioimidate species-facilitates new modes of reactivity and new synthetic abilities. Indeed, the urea class of H-bond donors has been shown to be more active than their corresponding thioureas. The imidate mechanism remains highly active in polar solvents and exhibits remarkable control-and 'living' behavior-under solvent-free conditions, and a broad range of temperatures is accessible. The advancements in synthetic abilities have all evolved through a greater understanding of reaction mechanism. Through the continued synergistic advances of catalysis and material, the (thio)urea class of catalyst can find use in a host of potential applications, research and industrial environments.
Publication Title, e.g., Journal
Organic and Biomolecular Chemistry
Dharmaratne, Nayanthara U., Jinal U. Pothupitiya, and Matthew K. Kiesewetter. "The mechanistic duality of (thio)urea organocatalysts for ring-opening polymerization." Organic and Biomolecular Chemistry 17, 13 (2019): 3305-3313. doi: 10.1039/c8ob03174f.