Chemistry of Trichlorosilyl Enolates. 1. New Reagents for Catalytic, Asymmetric Aldol Additions

Denmark, Scott E.; Winter, Stephen B.D.; Su, Xiping; Wong, Ken‐Tsung

doi:10.1021/ja9606539

Cited by 183 publications

(73 citation statements)

References 20 publications

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“…[316] Unlike allylic trichlorosilanes, these enol ethers possessed sufficient nucleophilicity to undergo rapid, uncatalyzed addition reactions with aromatic, olefinic, and aliphatic aldehydes as well as ketones. The binding of the weakly Lewis basic aldehyde provided sufficient activation for the aldol reaction.…”

Section: Lewis Base Catalyzed Aldolization With Enoxytrichlorosilanesmentioning

confidence: 99%

Lewis Base Catalysis in Organic Synthesis

2008

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The legacy of Gilbert Newton Lewis (1875-1946) pervades the lexicon of chemical bonding and reactivity. The power of his concept of donor-acceptor bonding is evident in the eponymous foundations of electron-pair acceptors (Lewis acids) and donors (Lewis bases). Lewis recognized that acids are not restricted to those substances that contain hydrogen (Brønsted acids), and helped overthrow the "modern cult of the proton". His discovery ushered in the use of Lewis acids as reagents and catalysts for organic reactions. However, in recent years, the recognition that Lewis bases can also serve in this capacity has grown enormously. Most importantly, it has become increasingly apparent that the behavior of Lewis bases as agents for promoting chemical reactions is not merely as an electronic complement of the cognate Lewis acids: in fact Lewis bases are capable of enhancing both the electrophilic and nucleophilic character of molecules to which they are bound. This diversity of behavior leads to a remarkable versatility for the catalysis of reactions by Lewis bases.

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Section: Lewis Base Catalyzed Aldolization With Enoxytrichlorosilanesmentioning

confidence: 99%

Lewis Base Catalysis in Organic Synthesis

2008

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“…[316] Anders als Allyltrichlorsilane sind diese Enolether nucleophil genug, um ohne Zusatz eines Katalysators rasch an aromatische, olefinische und aliphatische Aldehyde und Ketone zu addieren; die Bindung des schwach Lewis-basischen Aldehyds reicht zur Aktivierung der Aldolreaktion aus. Die Zugabe des chiralen Phosphoramid-Kata- lysators 258 führte mit einer begrenzten Zahl von Substraten zu einer mäßigen asymmetrischen Induktion.…”

Section: Lewis-base-katalysierte Aldolisierung Mit Enoxytrichlorsilanenunclassified

Lewis‐Base‐Katalyse in der organischen Synthese

2008

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Das Erbe von Gilbert Newton Lewis (1875–1946) ist im Wörterbuch der chemischen Bindung und Reaktivität allgegenwärtig. Die Bedeutung seines Konzepts der Donor‐Akzeptor‐Bindung kommt in den eponymen Grundbegriffen für Elektronenpaarakzeptoren (Lewis‐Säuren) und ‐donoren (Lewis‐Basen) zum Ausdruck. Lewis erkannte, dass Säuren nicht automatisch Wasserstoff enthalten müssen (Brønsted‐Säuren) und trug so zum Sturz des “modernen Protonenkults” bei. Seine Entdeckung läutete zunächst die Entwicklung von Lewis‐Säuren als Reagentien und Katalysatoren für organische Reaktionen ein, in den letzten Jahren wurde aber offensichtlich, dass für diese Zwecke auch Lewis‐Basen eingesetzt werden können. Bezüglich der Beschleunigung chemischer Reaktionen ergänzen Lewis‐Basen die entsprechenden Lewis‐Säuren nicht nur elektronisch: Tatsächlich können Lewis‐Basen die Elektrophilie wie auch die Nucleophilie der Verbindungen verstärken, an die sie gebunden werden. Diese unterschiedliche Reaktivität resultiert in einer bemerkenswerten Vielfalt Lewis‐Base‐katalysierter Reaktionen.

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“…been extensively explored by Denmark et al 19,20 since the first report in 1996 (Scheme 7). 21 In the context of stereoselective aldol transformations, the electron-pair of a chiral Lewis base catalyst interacts with an acceptor silicon atom of the enolate making it more reactive. In addition, the new chiral complex should interact with the carbonyl oxygen of aldehyde producing aldol adducts in a stereoselective manner.…”

Section: Chiral Lewis Base Catalysis In Enantioselective Aldol Reactionsmentioning

confidence: 99%

Metal-catalyzed asymmetric aldol reactions

Dias¹,

Lucca²,

Ferreira³

et al. 2012

J. Braz. Chem. Soc.

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A reação aldólica é uma das ferramentas mais poderosas e versáteis para a construção de ligações C−C. Tradicionalmente, esta reação foi desenvolvida em sua versão estequiométrica, no entanto, grandes esforços no desenvolvimento de catalisadores quirais para reações aldólicas foram realizados nos últimos anos. Desta forma, neste artigo de revisão, é discutido o desenvolvimento de catalisadores metálicos em reação aldólica do tipo Mukaiyama, reação aldólica redutiva e reação aldólica direta. Além disto, a aplicação destes catalisadores na síntese total de moléculas complexas será abordada.The aldol reaction is one of the most powerful and versatile methods for the construction of C−C bonds. Traditionally, this reaction was developed in a stoichiometric version; however, great efforts in the development of chiral catalysts for aldol reactions were performed in recent years. Thus, in this review article, the development of metal-mediated chiral catalysts in Mukaiyama-type aldol reaction, reductive aldol reaction and direct aldol reaction are discussed. Moreover, the application of these catalysts in the total synthesis of complex molecules is discussed.

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Chemistry of Trichlorosilyl Enolates. 1. New Reagents for Catalytic, Asymmetric Aldol Additions

Cited by 183 publications

References 20 publications

Lewis Base Catalysis in Organic Synthesis

Lewis Base Catalysis in Organic Synthesis

Lewis‐Base‐Katalyse in der organischen Synthese

Metal-catalyzed asymmetric aldol reactions

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