P(MeNMCH2CH2)3N: an effective catalyst for trimethylsilycyanation of aldehydes and ketones

Wang, Zhigang; Fetterly, Brandon M.; Verkade, John G.

doi:10.1016/s0022-328x(01)01436-x

Cited by 59 publications

(26 citation statements)

References 64 publications

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“…Other highly nucleophilic Lewis bases such as Verkades phosphatrane [270] and N-heterocyclic carbenes [271] have been assayed for their ability to promote silylcyanation, thus far only with achiral catalysts. [272] Imidazol-2-ylidene derivatives bearing bulky substituents on the nitrogen atoms (tert-butyl, mesityl, adamantyl) are highly effective catalysts, less than 1 mol % is needed to convert both aldehydes and ketones rapidly into the TMS-cyanohydrins at room temperature.…”

Section: Neutral Lewis Basesmentioning

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: Neutral Lewis Basesmentioning

confidence: 99%

Lewis Base Catalysis in Organic Synthesis

2008

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“…[ Andere hoch nucleophile Lewis-Basen wie Verkades Phosphatran [270] und N-heterocyclische Carbene [271] wurden ebenfalls auf ihre Fähigkeit zur Beschleunigung der Cyanosilylierung untersucht, bisher wurden aber nur achirale Katalysatoren geprüft. [272] Imidazol-2-yliden-Derivate mit raumfüllenden Substituenten an den Stickstoffatomen (tert-Butyl, Mesityl, Adamantyl) sind hoch effizient: Schon weniger als 1 Mol-% des Katalysators überführt Aldehyde und Ketone bei Raumtemperatur rasch in die TMS-Cyanhydrine.…”

Section: Alkylierung Von Enolatenunclassified

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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“…It is of particular interest to note that by-products such as those which could be produced by desilylation or benzoin condensation were not observed in all of the reactions studied. [58,59] In the next step, the procedure was further explored by conversion of aliphatic or aromatic ketones into their corresponding cyanohydrin trimethylsilyl ethers (5p-v) in high yields within short reaction time (entries [16][17][18][19][20][21][22]. In general, ketones required longer reaction times compared with aldehydes due to increasing the steric hindrance around the carbonyl functional group.…”

Section: Resultsmentioning

confidence: 99%

Organocatalytic synthesis of cyanohydrin trimethylsilyl ethers by potassium 4‐benzylpiperidinedithiocarbamate under solvent‐free conditions

Dekamin

Alizadeh

Naimi-Jamal

2009

Applied Organom Chemis

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Potassium 4-benzylpiperidinedithiocarbamate was found to be an efficient organocatalyst for facile addition of trimethylsilyl cyanide to a wide variety of aldehydes and ketones to afford corresponding cyanohydrin trimethylsilyl ethers in high to quantitative yields. The reaction proceeded smoothly by employing 2.0 mol% PBPDC loading under mild conditions at room temperature within a very short reaction time.

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P(MeNMCH2CH2)3N: an effective catalyst for trimethylsilycyanation of aldehydes and ketones

Cited by 59 publications

References 64 publications

Lewis Base Catalysis in Organic Synthesis

Lewis Base Catalysis in Organic Synthesis

Lewis‐Base‐Katalyse in der organischen Synthese

Organocatalytic synthesis of cyanohydrin trimethylsilyl ethers by potassium 4‐benzylpiperidinedithiocarbamate under solvent‐free conditions

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