Direct Catalytic Asymmetric Addition of Allyl Cyanide to Ketones

Yazaki, Ryo; Kumagai, Naoya; Shibasaki, Masakatsu

doi:10.1021/ja900001u

Cited by 101 publications

(31 citation statements)

References 53 publications

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“…Nucleophilic addition to benzylidene malononitrile, a carbonyl surrogate, [23] proceeds well, as does the addition of the electrophiles propylene oxide and diphenyl disulphide (Table 1, entries [15][16][17]. Cyclohexenone is attacked selectively at the carbonyl carbon (Table 1, entry 11), which is likely a consequence of strong chelation between the alkoxymagnesium intermediate and the p-electrons of the nitrile, [24] which prevents equilibration to the more stable conjugate adduct.…”

Section: Resultsmentioning

confidence: 99%

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Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies

Nath

Fleming

2012

Chemistry A European J

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Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl-metal exchange to afford N- or C-metalated nitriles. Sulfinyl-magnesium exchange-alkylations efficiently install quaternary and tertiary centers, even in the case of tertiary sulfinylnitriles that contain a highly acidic methine proton. α-Sulfinylalkenenitriles afford moderately nucleophilic magnesiated nitriles, and the reactivity can be dramatically increased by conversion to the corresponding magnesiates. The sulfinyl-metal exchange is extremely fast, proceeds efficiently with quaternary, tertiary, and vinylic α-sulfinylnitriles, and exhibits an exceptional functional group tolerance in nitrile alkylations.

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Section: Resultsmentioning

confidence: 99%

“…Several ingenious catalysts and reagent systems have been designed to address the deprotonation, and alkylation, of acetonitrile [14] (Scheme 2, 7! 8) and activated alkanenitriles [15] (Scheme 2, 8!9; R 1 = aryl or vinyl) with mild base or base-catalyst combinations. The…”

Section: Introductionmentioning

confidence: 99%

Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies

Nath

Fleming

2012

Chemistry A European J

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“…[37] Im Unterschied zu der für Ketimine beobachteten a-Addition fand lediglich g-Addition statt, bei der die entsprechenden tertiären Homoallylalkohole mit hervorragenden Enantioselektivitäten und vollständiger Z-Selektivität im Fall von Arylmethylketonen entstanden. [37] Im Unterschied zu der für Ketimine beobachteten a-Addition fand lediglich g-Addition statt, bei der die entsprechenden tertiären Homoallylalkohole mit hervorragenden Enantioselektivitäten und vollständiger Z-Selektivität im Fall von Arylmethylketonen entstanden.…”

Section: Angewandte Chemieunclassified

Cyanoalkylierung: Alkylnitrile in katalytischen C‐C‐Kupplungen

López

Palomo

2015

Angewandte Chemie

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Alkylnitrile zählen zu den am weitesten verbreiteten stickstoffhaltigen Verbindungen, und sie werden vielfach in Reaktionen eingesetzt, die die Umwandlung der Nitrilgruppe in andere Funktionalitäten beinhalten. Ihre Verwendung als Kohlenstoff‐Pronucleophile in Kohlenstoff‐Kohlenstoff‐Kupplungen wurde jedoch durch Schwierigkeiten erschwert, die hauptsächlich mit der katalytischen Erzeugung aktiver Spezies wie α‐Cyanocarbanionen und/oder metallierter Nitrile im Zusammenhang stehen. In neuesten Untersuchungen wurden nun mehrere Aktivierungsarten für Alkylnitrile entwickelt. Dieser Kurzaufsatz veranschaulicht diese Erkenntnisse, die die Grundlage für praktische und konzeptionell neue katalytische direkte Cyanoalkylierungsmethoden bilden.

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“…Cu-based systems have proven to be efficient catalysts [20,29]. The use of multifunctional Cu-based catalysts has been shown to promote efficiently the asymmetric addition of allyl cyanides 23 to activated imines 22 [31] and ketones [32] to yield 24 with a tetrasubstituted stereogenic center via an elegant proton-transfer/C-C bond-forming process. The use of multifunctional Cu-based catalysts has been shown to promote efficiently the asymmetric addition of allyl cyanides 23 to activated imines 22 [31] and ketones [32] to yield 24 with a tetrasubstituted stereogenic center via an elegant proton-transfer/C-C bond-forming process.…”

Section: 2-additionsmentioning

confidence: 99%

An Overview of Recent Developments in Metal‐Catalyzed Asymmetric Transformations

Sandoval¹,

Noyori²,

Zhou³

et al. 2012

Organic Chemistry – Breakthroughs and Perspectives

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IntroductionCatalysis is the most efficient means to bring about a chemical transformation, since the catalyst used is in principle not consumed in the process and can continuously catalyze a given process to generate a product. When a metal catalyst is employed, the catalysis itself generally stems from the inherent properties of the given metal(s) -Lewis acidity, variable oxidation states, coordination sphere properties, and so on. For metal-based molecular catalysis, however, the ligand frameworks about the metal center can have a dramatic effect on the stability and catalytic performance, and/or actively participate through metal-ligand cooperative processes. The use of chiral ligands generates a chiral 3D environment that effectively controls the stereo-outcome of the chemical transformation, thus giving rise to asymmetric catalysis. Such strategies have been instrumental in the development of modern synthetic strategies at the academic and industrial levels, and constitute a cornerstone for modern organic syntheses.This chapter aims to give a general overview of the types of metal-catalyzed processes currently possible, with emphasis on the catalytic transformation itself. Only representative examples from the last decade are given to highlight the catalytic process without aiming to be comprehensive [1]. More emphasis is given to C-C bond-forming metal-catalyzed asymmetric syntheses due to the rapid developments in this area in recent years. Mostly intermolecular processes are given as examples and typically the results presented are under optimum conditions and represent the highest efficiency and selectivity obtained. It should be mentioned that a similar chapter using different authors and examples may have been used to illustrate advances in a given area, which is a tribute to the excellence and scope of contemporary research advancing asymmetric catalysis.Contributions where the metal is involved as a (chiral) reagent or systems where enantioselection stems from substrate control or use of chiral auxiliaries were not considered. Catalytically active supramolecular assemblies where metals act as linkers or transformations involving metal-containing enzymes were judged inappropriate. Similarly, selective metal-catalyzed polymerization processes and concurrent breakthroughs in organocatalysis are not included.

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Direct Catalytic Asymmetric Addition of Allyl Cyanide to Ketones

Cited by 101 publications

References 53 publications

Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies

Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies

Cyanoalkylierung: Alkylnitrile in katalytischen C‐C‐Kupplungen

An Overview of Recent Developments in Metal‐Catalyzed Asymmetric Transformations

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