Transition-Metal-Catalyzed Carbenoid Reactions of Sulfonium Ylides

Müller, Paul; Fernández, Daniel; Nury, Patrice; Rossier, Jean-Claude

doi:10.1002/(sici)1522-2675(19990609)82:6<935::aid-hlca935>3.0.co;2-x

Cited by 65 publications

(42 citation statements)

References 7 publications

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“…Obwohl bereits 1966 das erste Beispiel für die Erzeugung eines Metallcarbens aus Schwefelyliden mit CuSO 4 als Katalysator beschrieben wurde, verliefen inter‐ und intramolekulare Cyclopropanierungen von Schwefelyliden in Gegenwart chiraler Rhodium‐ oder Kupferkatalysatoren zu 104′ und 108 bisher wenig erfolgreich (Schema ) …”

Section: Phenyliodonium‐ Und Sulfoniumylideunclassified

Neue Ansätze für die Synthese von Metallcarbenen

Jia

2016

Angewandte Chemie

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Metallcarbene sind vielseitige Verbindungen, deren Reaktivität sowohl durch das Metall als auch den Liganden gesteuert werden kann. Zur Synthese von Metallcarbenen nutzt man im Allgemeinen die Stickstoff‐Eliminierung von Diazoverbindungen, die allerdings häufig instabil, explosiv und toxisch sind, was ihren Einsatz in großskaligen Synthesen einschränkt. Demzufolge gibt es eine intensive Suche nach nachhaltigen und ungefährlichen Ersatzsubstraten für die zuverlässige Herstellung von Metallcarbenen. In diesem Aufsatz fassen wir die wichtigsten Fortschritte bei der Erzeugung, katalytischen Reaktionen und der Selektivitätskontrolle von Metallcarbenen zusammen, die nicht aus Diazoverbindungen gebildet wurden.

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Section: Phenyliodonium‐ Und Sulfoniumylideunclassified

Neue Ansätze für die Synthese von Metallcarbenen

Jia

2016

Angewandte Chemie

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“…The cyclopropanation reaction between sulfonium ylides and olefins in the presence of chiral rhodium and copper catalysts was first described by Müller et al48a,48b The reaction of ethyl diphenylsulfonium acetate ( 17 ; an equivalent carbene precursor of the commercially available ethyl diazoacetate) and styrene in the presence of the chiral rhodium salts 18 , 19 , or 20 led to cyclopropanes in yields of 34–47 % (Table 5). The cis ‐ and trans ‐cyclopropanes 21 and 22 were formed in a ratio of approximately 1:1 and with poor enantioselectivities, varying from 2 to 48 % ee .…”

Section: Metal‐catalyzed Insertion Reactions Of Sulfonium and Sulfmentioning

confidence: 99%

Sulfoxonium and Sulfonium Ylides as Diazocarbonyl Equivalents in Metal‐Catalyzed Insertion Reactions

2013

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Since the pioneering contribution of Corey and Chaykovsky in 1965, sulfoxonium and sulfonium ylides have proven to be versatile intermediates in organic synthesis. One of their important applications, though not yet throughly investigated, is their substitution of diazocarbonyl compounds as safer carbene precursors. This microreview provides an overview and recent applications of sulfoxonium and sulfonium ylides in inter‐ and intramolecular metal‐catalyzed insertion reactions. It also plans to illustrate the promising synthetic utility of these stable carbene precursors in industry, mitigating potential safety problems generally encountered when the equivalent diazo compounds are employed. Moreover, it aims to inspire new contributions to this exciting growing area, especially in catalytic asymmetric reactions.

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“…Among the many synthetic strategies reported, cyclopropanation of electron-rich alkenes is often performed using a transition-metal-catalyzed decomposition of diazoalkanes (diazodecomposition/carbene insertion) 4 or through halomethylmetal (Zn, Sm, Al)mediated reactions. 5,6 In general, the preparation of cyclopropylcarboxylic acid derivatives involves reacting an alkyl diazoacetate with an alkene using a transition-metal-containing catalyst (i.e., Cu, Со, Ru, Pd, or Rh). [7][8][9] However, electron-deficient alkenes are normally not reactive under these conditions and for the introduction of functionalized cyclopropyl motifs, a Michael-type addition of a nucleophilic alkylidene reagent is preferable.…”

Section: Introductionmentioning

confidence: 99%

Observation of a Tricyclic[4.1.0.0^2,4]heptane During a Michael Addition-Ring Closure Reaction and a Computational Study on Its Mechanism of Formation

et al. 2017

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We describe the formation of a bis-cyclopropane product, a tricyclic[4.1.0.0]heptane, that is formed during a Johnson-Corey-Chaykovsky reaction on a cyclopentenone. Two (of four possible) bicyclic products are selectively formed by addition of a COOEt-stabilized sulfur ylide onto the Michael acceptor. The tricyclic product is formed subsequently via a retro Michael elimination of a hindered ether followed by addition of a further cyclopropyl moiety, affecting only one of the two bicyclic products initially formed. The experimental reaction outcome was rationalized using density functional theory (DFT), investigating the different Michael-addition approaches of the sulfur ylide, the transition state (TS) energies for the formation of possible zwitterionic intermediates and subsequent reactions that give rise to cyclopropanation. Selective formation of only two of the four possible products occurs due to the epimerization of unreactive intermediates from the other two pathways, as revealed by energy barrier calculations. The formation of the tricyclic product was rationalized by evaluation of energy barriers for proton abstraction required to form the intermediate undergoing the second cyclopropanation. The selectivity-guiding factors discussed for the single and double cyclopropanation of this functionalized Michael-acceptor will be useful guidelines for the synthesis of future singly and doubly cyclopropanated compounds.

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Transition-Metal-Catalyzed Carbenoid Reactions of Sulfonium Ylides

Cited by 65 publications

References 7 publications

Neue Ansätze für die Synthese von Metallcarbenen

Neue Ansätze für die Synthese von Metallcarbenen

Sulfoxonium and Sulfonium Ylides as Diazocarbonyl Equivalents in Metal‐Catalyzed Insertion Reactions

Observation of a Tricyclic[4.1.0.0^2,4]heptane During a Michael Addition-Ring Closure Reaction and a Computational Study on Its Mechanism of Formation

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Transition-Metal-Catalyzed Carbenoid Reactions of Sulfonium Ylides

Cited by 65 publications

References 7 publications

Neue Ansätze für die Synthese von Metallcarbenen

Neue Ansätze für die Synthese von Metallcarbenen

Sulfoxonium and Sulfonium Ylides as Diazocarbonyl Equivalents in Metal‐Catalyzed Insertion Reactions

Observation of a Tricyclic[4.1.0.02,4]heptane During a Michael Addition-Ring Closure Reaction and a Computational Study on Its Mechanism of Formation

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Observation of a Tricyclic[4.1.0.0^2,4]heptane During a Michael Addition-Ring Closure Reaction and a Computational Study on Its Mechanism of Formation