Enantioselective Strecker Reactions between Aldimines and Trimethylsilyl Cyanide Promoted by Chiral <i>N</i>,<i>N′</i>‐Dioxides

Jiao, Zhigang; Feng, Xiaoming; Liu, Bo; Chen, Fuxue; Zhang, Guolin; Jiang, Yaozhong

doi:10.1002/ejoc.200300319

Cited by 95 publications

(27 citation statements)

References 72 publications

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“…[16] The activated nucleophile would attack the highly polarized C=N of ketimine 1 from a less stereohindered direction to give the desired product. Subsequently, elimination of the catalyst furnished the corresponding adduct 2 [17] and regenerated 3 e and PBAP (Scheme 3, step III).…”

Section: Resultsmentioning

confidence: 99%

Facile and Efficient Enantioselective Strecker Reaction of Ketimines by Chiral Sodium Phosphate

Shen

Liu

Cai

et al. 2009

Chemistry A European J

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102

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A facile and efficient enantioselective Strecker reaction of ketimines catalyzed by a chiral alkali-metal salt has been developed. When 10 mol % BNPNa (BNP = 1,1'-binaphthyl-2,2'-diylphosphate) prepared in situ and 10 mol % para-tert-butyl-ortho-adamantylphenol (PBAP) were introduced into the reaction, up to 96% yield and up to 95% ee (ee = enantiomeric excess) were obtained. Both aliphatic and aromatic ketimines, especially sterically bulky cyclic ketimines derived from beta-acetonaphthone, alpha-indanone, and alpha-tetralone were found suitable for this reaction. On the basis of the experimental results and previous reports, trimethylsilyl cyanide (TMSCN) was indicated to be the real reactive nucleophile despite the existence of PBAP, and a possible working model was proposed to explain the origin of the asymmetric induction. The facile availability of 1,1'-binaphthyl-2,2'-diylphosphoric acid (BNPH) and the simplicity of the procedure are beneficial for practical applications.

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Section: Resultsmentioning

confidence: 99%

Facile and Efficient Enantioselective Strecker Reaction of Ketimines by Chiral Sodium Phosphate

Shen

Liu

Cai

et al. 2009

Chemistry A European J

Self Cite

102

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“…75.0-97.5:25.0-2.5). [278] Hou and co-workers employed CsF to promote the addition of TMSCN to enolizable, aliphatic sulfinamines (aromatic sulfinamines fragment to 4-TolSCN).…”

Section: Strecker Reaction With Tmscnmentioning

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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“…Außerdem liegen einige Berichte über Lewis-Base-katalysierte Strecker-Reaktionen vor. In einer dieser Reaktionen wird ein chirales N-Oxid verwendet, [278] die anderen nutzen achirale Lewis-Basen und ein chirales Sulfinylimin. [279] Im ersten Fall beschleunigt eine stöchiometrische Menge (R)-3,3'-Dimethyl-2,2'-bis-chinolin-N,N'-dioxid die Addition von TMSCN an die N-Benzhydrylimine aromatischer Aldehyde, aber selbst bei dieser Katalysatorkonzentration dauern die Reaktionen 1-4 Tage.…”

Section: Strecker-reaktion Mit Tmscnunclassified

“…75:25-97.5:2.5). [278] Hou und Mitarbeiter verwendeten CsF, um die Addition von TMSCN an enolisierbare aliphatische Sulfinamine zu beschleunigen (aromatische Sulfinamine zerfallen zu 4-TolS-CN).…”

Section: Strecker-reaktion Mit Tmscnunclassified

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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Enantioselective Strecker Reactions between Aldimines and Trimethylsilyl Cyanide Promoted by Chiral N,N′‐Dioxides

Cited by 95 publications

References 72 publications

Facile and Efficient Enantioselective Strecker Reaction of Ketimines by Chiral Sodium Phosphate

Facile and Efficient Enantioselective Strecker Reaction of Ketimines by Chiral Sodium Phosphate

Lewis Base Catalysis in Organic Synthesis

Lewis‐Base‐Katalyse in der organischen Synthese

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