Enantioselective protonations: fundamental insights and new concepts
Tetrahedron AsymmetryPublished 1 November 2004
Lucette Duhamel, Pierre Duhamel, Jean‐Christophe Plaquevent
Citations203
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Abstract
This review deals with the main results obtained in the field of enantioselective protonations. This method allows easy access to various enantiomerically enriched compounds starting from either the corresponding racemic mixture (deracemization process) or various prochiral precursors. Discussions about different factors governing the stereoselectivity as well as a compilation of literature data are given.
Keywords
Chemistry
Medical Entomology and ZoologyStereochemistry of Organic Compounds
2,599 Citations1962Samuel H. Wilen, Lewis N. Mander +1 more
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125 Citations1987Howard E. Zimmerman
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The Journal of Organic Chemistry.alpha. Anions of carboxylic acids. II. Formation and alkylation of .alpha.-metalated aliphatic acids
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Journal of the American Chemical SocietyStudies in nuclear resonance spectroscopy. 14. Characterization and structures of lithioisobutyrophenone aggregates in ether solvents
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100 Citations1987Paul G. Williard, Mark J. Hintze
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93 Citations1985Paul G. Williard, Gene B. Carpenter
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Journal of the American Chemical SocietyLewis Acid-Induced Internal Proton Return in Enolate Complexes with Chiral Amines
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Angewandte Chemie International Edition in EnglishEnantioselective Protonation of Carbanions with Chiral Proton Sources
81 Citations1987Uwe Gerlach, Siegfried Hünig
Journal of the American Chemical SocietyDeracemization by enantioselective protonation. A new method for the enantiomeric enrichment of .alpha.-amino acids
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Tetrahedron AsymmetryEnantioselective protonation of achiral lithium enolates using a chiral amine in the presence of lithium bromide
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71 Citations1994Charles Fehr, José Galindo
Tetrahedron LettersHighly enantioselective protonation of photodienols an unusual substituent effect on the induced chirality
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The Journal of Organic ChemistryEnantioselective Protonation of Enolates: Novel Chiral Proton Sources and Remarkable Effects of the Countercation
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Angewandte Chemie International Edition in EnglishFunctional Groups at Concave Sites: Asymmetric Alkylation of Esters with Very High Stereoselectivity and Reversal of Configuration by Change of Solvent
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Chemical CommunicationsA study of asymmetric protonation with chiral β-hydroxy sulfoxides. Asymmetric synthesis of (–)-epibatidine
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Journal of the American Chemical SocietyLewis acid-induced internal proton return: enantiocontrolled protonation of an amide enolate
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Tetrahedron LettersDeracemization by enantioselective protonation IV an improved method for the enantiomeric enrichment of α-aminoacids using metalation by means of chiral amides
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The Journal of Organic ChemistryCatalytic Asymmetric Protonation of Amide Enolates: Optimization of Kinetic Acidity in the Catalytic Cycle
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Angewandte Chemie International Edition in EnglishAsymmetric Protonation of Enolates
55 Citations1990Dominique Potin, Kevin M. Williams +1 more
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Journal of the American Chemical SocietyNuclear magnetic resonance spectroscopy. XI. Proton spectroscopy of lithioisobutyrophenone and its complexes with lithium chloride and bromide
52 Citations1973L. M. Jackman, Robert C. Haddon
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52 Citations1991Kazutsugu Matsumoto, Hiromichi Ohta
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52 Citations1985Lloyd M. Jackman, T. S. DUNNE
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Helvetica Chimica ActaSyntheses of the Enantiomers of γ‐Cyclogeranic Acid, γ‐Cyclocitral, and γ‐Damascone: Enantioselective protonation of enolates
51 Citations1995Charles Fehr, José Galindo
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Mixed aggregates between lithium enolates and lithium hexamethyldisilazide (LiHMDS) have been studied in THF using UV-vis spectroscopy and the rate constants for the mixed aggregates, k(Mixed), are substantially smaller than those of the monomeric enolate.
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47 Citations1998Akira Yanagisawa, T. Kikuchi +2 more
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45 Citations1996Yutaka Nakamura, Seiji Takeuchi +2 more
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43 Citations1977Lucette Duhamel, Jean‐Christophe Plaquevent
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43 Citations1998Lásʐló Tőke, Péter Bakó +3 more
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43 Citations1994Françoise Hénin, Athanase M'Boungou-M'Passi +2 more
Nachrichten aus Chemie Technik und LaboratoriumEnantioselektive Deprotonierungen und Protonierungen
43 Citations1991
Angewandte Chemie International Edition in EnglishEnantioselective Protonation of Simple Enolates: Chiral Imide as a Chiral Proton Source
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Tetrahedron AsymmetryEnantioselective protonation of samarium enolates by a C2-symmetric chiral diol
41 Citations1994Seiji Takeuchi, Akiko Ohira +3 more
Journal of Synthetic Organic Chemistry JapanApproaches to Catalytic Asymmetric Formation and Reactions of Lithium Enolates.
40 Citations1995Kenji Koga, Mitsuru Shindo
Journal of the American Chemical SocietyEnantioselective lactonization of sodium 4-hydroxypimelate under abiological conditions
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37 Citations1998Kazuaki Ishihara, Hiroko Nakamura +2 more
The Journal of Organic ChemistryCatalytic Enantioselective Protonation of Lithium Enolates with Chiral Imides
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