biostudies-literatureBannin TJNational Institute of General Medical SciencesNIGMS NIH HHS5481-5486https://www.ebi.ac.uk/biostudies/studies/S-EPMC4863702biostudies-literatureUnknown48(16)Organocatalysts typically used for the ring-opening polymerization (ROP) of cyclic ester monomers are applied to a thiolactone, <i>ε</i>-thiocaprolactone (tCL). In the absence of an H-bond donor, a nucleophilic polymerization mechanism is proposed. Despite the decreased ability of thioesters and thiols (versus esters and alcohols) to H-bond, H-bonding organocatalysts-a thiourea in combination with an H-bond accepting base-are also effective for the ROP of tCL. The increased nucleophilicity of thiols (versus alcohols) is implicated in the increased <i>M</i>_w/<i>M</i>_n of the poly(thiocaprolactone) versus poly(caprolactone), but deleterious transesterification is suppressed in the presence of a thiourea. The thioester monomer, tCL, is shown to be thermodynamically similar to <i>ε</i>-caprolactam but kinetically similar to <i>ε</i>-caprolactone.MacromoleculesPoly(thioester) by Organocatalytic Ring-Opening Polymerization.PMC48637028 P20 GM103430-12P20 GM103430Bannin TJKiesewetter MKfalsePoly(thioester) by Organocatalytic Ring-Opening Polymerization.Organocatalysts typically used for the ring-opening polymerization (ROP) of cyclic ester monomers are applied to a thiolactone, <i>ε</i>-thiocaprolactone (tCL). In the absence of an H-bond donor, a nucleophilic polymerization mechanism is proposed. Despite the decreased ability of thioesters and thiols (versus esters and alcohols) to H-bond, H-bonding organocatalysts-a thiourea in combination with an H-bond accepting base-are also effective for the ROP of tCL. The increased nucleophilicity of thiols (versus alcohols) is implicated in the increased <i>M</i>_w/<i>M</i>_n of the poly(thiocaprolactone) versus poly(caprolactone), but deleterious transesterification is suppressed in the presence of a thiourea. The thioester monomer, tCL, is shown to be thermodynamically similar to <i>ε</i>-caprolactam but kinetically similar to <i>ε</i>-caprolactone.2015-01-01T00:00:00Z2015 Aug2025-04-22T06:22:27.556Z2019-03-27T02:13:29ZS-EPMC48637022718208510.1021/acs.macromol.5b01463