Bis- and Tris-Urea H-Bond Donors for Ring-Opening Polymerization: Unprecedented Activity and Control from an Organocatalyst
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A new class of H-bond donating ureas was developed for the ring-opening polymerization (ROP) of lactone monomers, and they exhibit dramatic rate acceleration versus previous H-bond mediated polymerization catalysts. The most active of these new catalysts, a tris-urea H-bond donor, is among the most active organocatalysts known for ROP, yet it retains the high selectivity of H-bond mediated organocatalysts. The urea cocatalyst, along with an H-bond accepting base, exhibits the characteristics of a "living" ROP, is highly active, in one case, accelerating a reaction from days to minutes, and remains active at low catalyst loadings. The rate acceleration exhibited by this H-bond donor occurs for all base cocatalysts examined. A mechanism of action is proposed, and the new catalysts are shown to accelerate small molecule transesterifications versus currently known monothiourea catalysts. It is no longer necessary to choose between a highly active or highly selective organocatalyst for ROP.
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The rate acceleration is proposed to arise from an "activated (thio)urea" mechanism in which each additional (thio)urea moiety enhances the acidity via intramolecular H-bond activation, supported by DFT calculations.
“The rate acceleration is proposed to arise from an “activated (thio)urea” mechanism in which each additional (thio)urea moiety enhances the acidity via intramolecular H-bond activation (Scheme 13), supported by DFT calculations.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [338]
Kiesewetter reported a series of bis- and tris-(thio)urea based H-bond donors, which exhibited dramatic rate acceleration compared to the mono-TU/amine systems, yet retaining the high selectivity for propagation over transesterification.
“Kiesewetter reported a series of bis-and tris-(thio)urea based H-bond donors (Scheme 13), which exhibited dramatic rate acceleration compared to the mono-TU/amine systems, yet retaining the high selectivity for propagation over transesterification. 337,338”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [338]
The most active one, a trisurea/MTBD, is approximately 100 times faster than mono-TU/MTBD for the ROP of CL, with equally good control on molecular weights and molecular weight distributions (Ð < 1.05).
“The most active one, a trisurea/MTBD, is approximately 100 times faster than mono-TU/MTBD for the ROP of CL, with equally good control on molecular weights and molecular weight distributions (Ð < 1.05).”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [338]
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- Authors
- Fastnacht, K. V., Spink, S. S., Dharmaratne, N. U., Pothupitiya, J. U., Datta, P. P., Kiesewetter, E. T., & Kiesewetter, M. K.
- Affiliations
- University of Rhode Island (US)
- Corresponding author
- Kiesewetter, Matthew K.
- Venue
- ACS Macro Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-08-03
- Volume
- 5
- Issue
- 8
- Pages
- 982-986
- ISSN
- 2161-1653 (ISSN-L)
- OpenAlex
- W2500824099
- Cited by
- 109
- References
- 38
- Citations by year
- 2026: 5 · 2025: 11 · 2024: 12 · 2023: 9 · 2022: 5 · 2021: 9 · 2020: 11 · 2019: 15 · 2018: 18 · 2017: 12 · 2016: 2
- FWCI
- 6.41
- Type
- journal article
- Language
- en
- Open access
- Licence
- cc-by-nc-nd
- Locations
- ACS Macro Letters (publishedVersion)
- PubMed (publishedVersion)
- Journal of Media Literacy Education (submittedVersion, cc-by-nc-nd)
- Journal of Media Literacy Education (submittedVersion, cc-by)
- Funders
- Division of Chemistry (CHE-1554830)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- ring-opening polymerization, lactone monomers, organocatalysis, living polymerization, transesterification, catalytic mechanism, catalyst selectivity
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