Cinchona Alkaloids as Stereoselective Organocatalysts for the Partial Kinetic Resolution Polymerization of rac-Lactide

Miyake, Garret M.; Chen, Eugene Y.-X.

doi:10.1021/ma2007199

Cited by 78biodegradable polymer synthesis and propertiesAsymmetric Synthesis and CatalysisAdvanced Polymer Synthesis and Characterization

Cinchona Alkaloids as Stereoselective Organocatalysts for the Partial Kinetic Resolution Polymerization of rac-Lactide

Miyake, Garret M., Chen, Eugene Y.-X.·2011·Macromolecules

DOI 10.1021/ma2007199

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Abstract

This work investigates, for the first time, cinchona alkaloids such as cinchonidine (CD) and β-isocupreidine (ICD) consisting of both a chiral nucleophilic amine catalyst site and an electrophilic hydroxy moiety, as bifunctional, stereoselective organocatalysts for the ring-opening polymerization (ROP) of l -lactide ( l -LA) and rac -lactide ( rac -LA). While the ROP of l -LA by CD is ineffective, the ROP of l -LA by ICD proceeds without noticeable epimerization, thus affording polylactide (PLA) with a quantitative isotacticity. The measured number-average molecular weight ( M n ) is much higher than the expected M n due to sluggish initiation by ICD, but when benzyl alcohol is added as an external protic initiator, the ROP is highly efficient and proceeds to high conversions without undesired transesterification reactions, thus producing PLA with a controlled M n and a narrow molecular weight distribution of 1.12. More significantly, the ROP of rac -LA by ICD/alcohol affords crystalline isotactic-rich, stereogradient PLA that exhibits multiple melting-transition temperatures as a result of a partial kinetic resolution polymerization that preferentially polymerizes l -LA and kinetically resolves d -LA. Overall, this study uncovers the first kinetic resolution polymerization of rac -LA by an organocatalyst.

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Chen developed a bifunctional catalyst that combines β-isocupreidine, a previously reported chiral ROP catalyst with low enantioselectivity (kL/kD = 4.4), and a chiral thiourea based on the binaphthyl scaffold.
“Chen developed a bifunctional catalyst that combines b-isocupreidine, a previously reported chiral ROP catalyst with low enantioselectivity (kL/kD = 4.4), 340 and a chiral thiourea based on the binaphthyl scaffold.341”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [340]

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Authors: Miyake, G. M., & Chen, E. Y.-X.
Affiliations: Colorado State University (US)
Corresponding author: Chen, Eugene Y.-X.
ORCID: Miyake, Garret M.
Chen, Eugene Y.-X.
Venue: Macromolecules
Publisher: American Chemical Society (ACS)
Published: 2011-05-12
Volume: 44
Issue: 11
Pages: 4116-4124
ISSN: 0024-9297 (ISSN-L)
1520-5835
DOI: 10.1021/ma2007199
OpenAlex: W2031291628
Cited by: 78
References: 51
Citations by year: 2026: 1 · 2025: 3 · 2024: 5 · 2023: 5 · 2022: 3 · 2021: 5 · 2020: 7 · 2019: 6 · 2018: 7 · 2017: 11 · 2016: 2 · 2015: 5 · 2014: 7 · 2013: 6 · 2012: 3
FWCI: 2.36
Type: journal article
Language: en
Open access: closed
Locations: Macromolecules (publishedVersion)
Funders: National Science Foundation
Topics: Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Keywords: cinchona alkaloids, cinchonidine, bifunctional catalysts, ring-opening polymerization, L-lactide, rac-lactide, polylactic acid, isotacticity, benzyl alcohol initiator, molecular weight distribution, epimerization

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Cinchona Alkaloids as Stereoselective Organocatalysts for the Partial Kinetic Resolution Polymerization of rac-Lactide

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