ArticleJournal of the American Chemical Society2017
Lithium Hexamethyldisilazide-Mediated Enolization of Highly Substituted Aryl Ketones: Structural and Mechanistic Basis of the E/Z Selectivities.
Article in Journal of the American Chemical Society, 2017. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 12 papers.
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Who cites it
12 citing papers in PubMed, 33 citations in OpenAlex.
- Regiodivergent Ring-Expansion of Oxindoles to Quinolinones.Journal of the American Chemical Society · 2024Article
- Carbon-Nitrogen Bond Formation Using Sodium Hexamethyldisilazide: Solvent-Dependent Reactivities and Mechanisms.Journal of the American Chemical Society · 2023Article
- Ketone Enolization with Sodium Hexamethyldisilazide: Solvent- and Substrate-DependentJournal of the American Chemical Society · 2021Article
- Global Diastereoconvergence in the Ireland-Claisen Rearrangement of Isomeric Enolates: Synthesis of Tetrasubstituted α-Amino Acids.Journal of the American Chemical Society · 2020Article
- Mechanistic insights into rhodium-catalyzed enantioselective allylic alkylation for quaternary stereogenic centers.Chemical science · 2020Article
- Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Acyclic α-Organic letters · 2020Article
- Asymmetric Hydrogenation of Unfunctionalized Tetrasubstituted Acyclic Olefins.Angewandte Chemie (International ed. in English) · 2020Article
- Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Protected Benzoin-Derived Enol Carbonates.Advanced synthesis & catalysis · 2020Article
- Article
- Palladium-catalyzed α,β-dehydrogenation of acyclic ester equivalents promoted by a novel electron deficient phosphinooxazoline ligand.Tetrahedron · 2019Article
- Palladium-catalyzed enantioselective decarboxylative allylic alkylation of fully substitutedChemical science · 2019Article
- Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates.Journal of the American Chemical Society · 2018Article
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Authors and funding
5 authors at 1 institution in 1 country.
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Abstract
Enolizations of highly substituted acyclic ketones used in the syntheses of tetrasubstituted olefin-based anticancer agents are described. Lithium hexamethyldisilazide (LiHMDS)-mediated enolizations are moderately Z-selective in neat tetrahydrofuran (THF) and E-selective in 2.0 M THF/hexane. The results of NMR spectroscopy show the resulting enolates to be statistically distributed ensembles of E,E-, E,Z-, and Z,Z-enolate dimers with subunits that reflect the selectivities. The results of rate studies trace the preference for E and Z isomers to tetrasolvated- and pentasolvated-monomer-based transition structures, respectively. Enolization using LiHMDS in N,N-dimethylethylamine or triethylamine in toluene affords a 65:1 mixture of LiHMDS-lithium enolate mixed dimers containing E and Z isomers, respectively. Spectroscopic studies show that condition-dependent complexation of ketone to LiHMDS occurs in trialkylamine/toluene. Rate data attribute the high selectivity exclusively to monosolvated-dimer-based transition structures.
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