Mechanistic Basis for High Reactivity of (salen)Co–OTs in the Hydrolytic Kinetic Resolution of Terminal Epoxides
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The (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides is a bimetallic process with a rate controlled by partitioning between a nucleophilic (salen)Co-OH catalyst and a Lewis acidic (salen)Co-X catalyst. The commonly used (salen)Co-OAc and (salen)Co-Cl precatalysts undergo complete and irreversible counterion addition to epoxide during the course of the epoxide hydrolysis reaction, resulting in quantitative formation of weakly Lewis acidic (salen)Co-OH and severely diminished reaction rates in the late stages of HKR reactions. In contrast, (salen)Co-OTs maintains high reactivity over the entire course of HKR reactions. We describe here an investigation of catalyst partitioning with different (salen)Co-X precatalysts and demonstrate that counterion addition to epoxide is reversible in the case of the (salen)Co-OTs. This reversible counterion addition results in stable partitioning between nucleophilic and Lewis acidic catalyst species, allowing highly efficient catalysis throughout the course of the HKR reaction.
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Recent advances in stereoselective epoxide polymerization support a bimetallic mechanism but feature the presence of nucleophiles.
“Recent advances in stereoselective epoxide polymerization also support a bimetallic mechanism but feature the presence of nucleophiles as well. 41-45”
From Mechanistic Studies of Redox-Switchable Copolymerization of Lactide and Cyclohexene Oxide by a Zirconium Complex (2017) · cites this paper as [44]
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Stereoselective Epoxide Polymerization and Copolymerization
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- Authors
- Nielsen, L. P. C., Zuend, S. J., Ford, D. D., & Jacobsen, E. N.
- Affiliations
- Harvard University (US)
- Corresponding author
- Jacobsen, Eric N.
- Venue
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-02-08
- Volume
- 77
- Issue
- 5
- Pages
- 2486-2495
- ISSN
- 0022-3263 (ISSN-L)
- 1520-6904
- PMC
- PMC3292627
- OpenAlex
- W1994551209
- Cited by
- 62
- References
- 27
- Citations by year
- 2026: 1 · 2025: 2 · 2024: 2 · 2023: 2 · 2022: 4 · 2021: 3 · 2020: 6 · 2019: 1 · 2018: 3 · 2017: 8 · 2016: 1 · 2015: 8 · 2014: 10 · 2013: 7 · 2012: 4
- FWCI
- 4.26
- Type
- journal article
- Language
- en
- Open access
- green
- europepmc.org
- Locations
- The Journal of Organic Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Europe PMC (PubMed Central) (acceptedVersion)
- PubMed Central (acceptedVersion)
- Digital Access to Scholarship at Harvard (DASH) (Harvard University) (submittedVersion, cc-by)
- Funders
- National Institute of General Medical Sciences (GM43214, R01GM043214, R37GM043214)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Inorganic and Organometallic Chemistry
- Keywords
- hydrolytic kinetic resolution, terminal epoxides, bimetallic catalysis, Lewis acidity, nucleophilic catalysis, epoxide hydrolysis, reaction mechanism
- MeSH terms
- Cobalt, Epoxy Compounds, Ethylenediamines, Hydrolysis, Kinetics, Organometallic Compounds, Molecular Structure
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