ArticleChemical science2014
Catalytic Kinetic Resolution of a Dynamic Racemate: Highly Stereoselective β-Lactone Formation by
Article in Chemical science, 2014. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 15 papers.
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Who cites it
15 citing papers in PubMed.
- Conformational Analysis Explores the Role of Electrostatic Nonclassical CF···HC Hydrogen Bonding Interactions in Selectively Halogenated Cyclohexanes.The Journal of organic chemistry · 2024Article
- EnantioconvergentOrganic letters · 2023Article
- Electrostatic Interactions in Asymmetric Organocatalysis.Accounts of chemical research · 2023Article
- Mechanism of a Dually Catalyzed Enantioselective Oxa-Pictet-Spengler Reaction and the Development of a Stereodivergent Variant.ACS catalysis · 2023Article
- Oxidative N-Heterocyclic Carbene Catalysis.Chemistry (Weinheim an der Bergstrasse, Germany) · 2023Review
- Dynamic kinetic resolution of γ,γ-disubstituted indole 2-carboxaldehydesChemical science · 2022Article
- Stereodivergent Nucleophilic Additions to Racemic β-Oxo Acid Derivatives: Fast Addition Outcompetes Stereoconvergence in the Archetypal Configurationally Unstable Electrophile.Journal of the American Chemical Society · 2021Article
- The Mechanism of N-Heterocyclic Carbene Organocatalysis through a Magnifying Glass.Chemistry (Weinheim an der Bergstrasse, Germany) · 2020Review
- Catalytic enantioselective synthesis of perfluoroalkyl-substituted β-lactonesChemical science · 2019Article
- Torsional steering as friend and foe: development of a synthetic route to the briarane diterpenoid stereotetrad.Organic & biomolecular chemistry · 2017Article
- Catalytic Asymmetric Synthesis of Ketene Heterodimer β-Lactones: Scope and Limitations.The Journal of organic chemistry · 2016Article
- Asymmetric Synthesis of β-Amino Amides by Catalytic Enantioconvergent 2-Aza-Cope Rearrangement.Journal of the American Chemical Society · 2015Article
- Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: mechanistic insight and synthetic application.Chemical communications (Cambridge, England) · 2015Article
- Enantioconvergent synthesis of functionalized γ-butyrolactones via (3 + 2)-annulation.Journal of the American Chemical Society · 2015Article
- Dynamic kinetic asymmetric cross-benzoin additions of β-stereogenic α-keto esters.Journal of the American Chemical Society · 2014Article
Corrections and comments
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Authors and funding
5 authors.
Funding
Abstract
This study describes the combined experimental and computational elucidation of the mechanism and origins of stereoselectivities in the NHC-catalyzed dynamic kinetic resolution (DKR) of α-substituted-β-ketoesters. Density functional theory computations reveal that the NHC-catalyzed DKR proceeds by two mechanisms, depending on the stereochemistry around the forming bond: 1) a concerted, asynchronous formal (2+2) aldol-lactonization process, or 2) a stepwise spiro-lactonization mechanism where the alkoxide is trapped by the NHC-catalyst. These mechanisms contrast significantly from mechanisms found and postulated in other related transformations. Conjugative stabilization of the electrophile and non-classical hydrogen bonds are key in controlling the stereoselectivity. This reaction constitutes an interesting class of DKRs in which the catalyst is responsible for the kinetic resolution to selectively and irreversibly capture an enantiomer of a substrate undergoing rapid racemization with the help of an exogenous base.
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Registered trials
Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.