Journal ArticleDOI
Designing Fluorinated Cinchona Alkaloids for Enantioselective Catalysis: Controlling Internal Rotation by a Fluorine‐Ammonium Ion gauche Effect (φNCCF)
Reads0
Chats0
TLDR
A fluoride-ammonium ion gauche effect constitutes a partial solution to the long-standing problem of governing internal rotations in cinchonium-based catalysts relying solely on a fluorine conformational effect.Abstract:
The C9 position of cinchona alkaloids functions as a molecular hinge, with internal rotations around the C8 C9 (tau(1)) and C9 C4' (tau(2)) bonds giving rise to four low energy conformers (1; anti-closed, anti-open, syn-closed, and syn-open). By substituting the C9 carbinol centre by a configurationally defined fluorine substituent, a fluorine-ammonium ion gauche effect (sigma(C-H) -> sigma(C-F)*; F-delta-...N+) encodes for two out of the four possible conformers (2). This constitutes a partial solution to the long-standing problem of governing internal rotations in cinchonium-based catalysts relying solely on a fluorine conformational effect.read more
Citations
More filters
Journal ArticleDOI
Monofluorination of Organic Compounds: 10 Years of Innovation.
Pier Alexandre Champagne,Justine Desroches,Jean Denys Hamel,Mathilde Vandamme,Jean-François Paquin +4 more
Journal ArticleDOI
Recent Developments in Asymmetric Phase-Transfer Reactions
Seiji Shirakawa,Keiji Maruoka +1 more
TL;DR: A wide variety of asymmetric transformations catalyzed by chiral onium salts and crown ethers have been developed for the synthesis of valuable organic compounds in the past several decades, especially in recent years.
Journal ArticleDOI
Modern Approaches for Asymmetric Construction of Carbon–Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs
Yi Zhu,Jianlin Han,Jiandong Wang,Norio Shibata,Mikiko Sodeoka,Vadim A. Soloshonok,Vadim A. Soloshonok,Jaime A. S. Coelho,F. Dean Toste +8 more
TL;DR: A comprehensive review of current research activity in asymmetric construction of quaternary C-F stereogenic centers is provided, including such general directions as asymmetric electrophilic fluorination via organocatalytic and transition-metal catalyzed reactions, asymmetric elaboration of fluorine-containing substrates via alkylations, Mannich, Michael, and aldol additions, cross-coupling reactions, and bioc atalytic approaches.
Journal ArticleDOI
The influence of fluorine in asymmetric catalysis
Dominique Cahard,Vincent Bizet +1 more
TL;DR: The subtle effects of fluorine atom(s) on the course of asymmetric reactions are outlined in this tutorial review and a comparative study of the stereochemical outcomes with reactions carried out in the presence of non-fluorinated analogues is presented.
Journal ArticleDOI
Neue Entwicklungen bei asymmetrischen Phasentransferreaktionen
Seiji Shirakawa,Keiji Maruoka +1 more
TL;DR: The Phasentransferkatalyse bildet eine effiziente Grundlage zur Einfuhrung praktischer Methoden in die organische Synthese, denn sie bietet mehrere Vorteile wie einfache Handhabung, milde Reaktionsbedingungen, die Eignung fur grostechnische Synthesen and ein umweltfreundliches Reaktionsystem as discussed by the authors.
References
More filters
Journal ArticleDOI
Understanding organofluorine chemistry. An introduction to the C–F bond
TL;DR: Fundamental aspects of the C-F bond are explored to rationalise the geometry, conformation and reactivity of individual organofluorine compounds.
Journal ArticleDOI
Privileged Chiral Catalysts
Tehshik P. Yoon,Eric N. Jacobsen +1 more
TL;DR: Drawing inspiration from natural catalysts, chemists have developed a variety of synthetic small-molecule catalysts that can achieve levels of selectivity approaching, and in some cases matching, those observed in enzymatic reactions.
Journal ArticleDOI
Recent advances in asymmetric phase-transfer catalysis.
Takashi Ooi,Keiji Maruoka +1 more
TL;DR: This work has shown that the use of chiral nonracemic onium salts and crown ethers as effective phase-transfer catalysts provides a reliable and general strategy for the practical asymmetric synthesis of highly valuable organic compounds.
Journal ArticleDOI
Recent development and application of chiral phase-transfer catalysts.
Takuya Hashimoto,Keiji Maruoka +1 more
Journal ArticleDOI
The Enantioselective Synthesis of α-Amino Acids by Phase-Transfer Catalysis with Achiral Schiff Base Esters
TL;DR: The development and application of chiral phase-transfer catalysis (PTC) for the enantioselective synthesis of optically active alpha-amino acid derivatives using achiral Schiff base esters developed in the author's laboratory and by others is reviewed.