ArticleJournal of the American Chemical Society2014
Enantioselective nucleophile-catalyzed synthesis of tertiary alkyl fluorides via the α-fluorination of ketenes: synthetic and mechanistic studies.
Article in Journal of the American Chemical Society, 2014. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 17 papers.
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Who cites it
17 citing papers in PubMed.
- Enantioselective isothiourea-catalysed α-fluorination of C1-ammonium enolates generated from arylesters.Journal of fluorine chemistry · 2025Article
- Enantioselective α-heterofunctionalization reactions of catalytically generated C1-Lewis base enolates.Tetrahedron chem · 2024Article
- Photochemical Wolff Rearrangement Initiated Generation and Subsequent α-Chlorination of C1 Ammonium Enolates.Organic letters · 2023Article
- Cooperative Palladium/Isothiourea Catalyzed Enantioselective Formal (3+2) Cycloaddition of Vinylcyclopropanes and α,β-Unsaturated Esters.Angewandte Chemie (International ed. in English) · 2022Article
- Enantioselective α-Chlorination Reactions of in Situ Generated C1 Ammonium Enolates under Base-Free Conditions.Organic letters · 2021Article
- Generation and Reactivity of C(1)-Ammonium Enolates by Using Isothiourea Catalysis.Chemistry (Weinheim an der Bergstrasse, Germany) · 2021Review
- Ligand-free iron-catalyzed benzylic C (spRSC advances · 2019Article
- Traversing Steric Limitations by Cooperative Lewis Base/Palladium Catalysis: An Enantioselective Synthesis of α-Branched Esters Using 2-Substituted Allyl Electrophiles.Angewandte Chemie (International ed. in English) · 2018Article
- Multiple roles of aryloxide leaving groups in enantioselective annulations employing α,β-unsaturated acyl ammonium catalysis.Chemical science · 2018Article
- Modern Approaches for Asymmetric Construction of Carbon-Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs.Chemical reviews · 2018Review
- Palladium-Catalyzed, Enantioselective α-Arylation of α-Fluorooxindoles.Organic letters · 2017Article
- Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis.Journal of the American Chemical Society · 2017Article
- Enantioselective fluorination of α-branched aldehydes and subsequent conversion to α-hydroxyacetalsChemical science · 2016Article
- Palladium-catalyzed enantioselective 1,1-fluoroarylation of aminoalkenes.Journal of the American Chemical Society · 2015Article
- Use of a new spirophosphine to achieve catalytic enantioselective [4 + 1] annulations of amines with allenes to generate dihydropyrroles.Journal of the American Chemical Society · 2015Article
- Advances in catalytic enantioselective fluorination, mono-, di-, and trifluoromethylation, and trifluoromethylthiolation reactions.Chemical reviews · 2015Review
- An in situ directing group strategy for chiral anion phase-transfer fluorination of allylic alcohols.Journal of the American Chemical Society · 2014Article
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3 authors.
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Abstract
The catalytic asymmetric synthesis of alkyl fluorides, particularly α-fluorocarbonyl compounds, has been the focus of substantial effort in recent years. While significant progress has been described in the formation of enantioenriched secondary alkyl fluorides, advances in the generation of tertiary alkyl fluorides have been more limited. Here, we describe a method for the catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C6F5ONa to furnish tertiary α-fluoroesters. Mechanistic studies are consistent with the hypothesis that the addition of an external nucleophile (C6F5ONa) is critical for turnover, releasing the catalyst (PPY*) from an N-acylated intermediate. The available data can be explained by a reaction pathway wherein the enantioselectivity is determined in the turnover-limiting transfer of fluorine from NFSI to a chiral enolate derived from the addition of PPY* to the ketene. The structure and the reactivity of the product of this proposed elementary step, an α-fluoro-N-acylpyridinium salt, have been examined.
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