Studies in Phosphinemethylene Chemistry. X. The Reaction of Organolithium Reagents with Alkyltriphenylphosphonium Halides. The Mechanism of Phosphinemethylene Formation<sup>1</sup>

Seyferth, Dietmar; Hughes, William B.; Heeren, James K.

doi:10.1021/ja01091a013

Cited by 38 publications

(11 citation statements)

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“…The reaction of activated acetylenes (2) with alkyl 2-nitroethanoates (25) in the presence of (1) leads to the corresponding functionalized isoxazoles (29) in good yields. It is conceivable that the initial event is the formation of a 1,3-dipolar intermediate from TPP and the acetylenic compound, and that this is subsequently protonated by the alkyl 2-nitroethanoate.…”

Section: Reaction Of Triphenylphosphine Dialkyl Acetylenedicarboxylamentioning

confidence: 99%

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Synthesis and Reactions of Stabilized Phosphorus Ylides

Ramazani

Kazemizadeh

Ahmadi³

et al. 2008

COC

106

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Stabilized phosphorus ylides, versatile intermediates in synthetic organic chemistry can be prepared by the novel reaction of dialkyl acetylenedicarboxylates (DAAD), triphenylphosphine (TPP) and acids such as phenols, imides, amides, enols, oximes and alcohols. The reaction involves an intermediate formed by the 1:1 conjugate addition reaction of the TPP to DAAD and concomitant protonation of the intermediate by an acid leads to vinyltriphenylphosphonium salts. The salts are unstable intermediates and converted to stabilized phosphorus ylides via Michael addition reaction. The stabilized phosphorus ylides are able to take part in the normal intramolecular Wittig reactions but they are not generally able to participate in the normal intermolecular Wittig reactions. The intermolecular Wittig reactions of the ylides are observed only with highly electron-poor carbonyl groups such as indane-1,2,3-trione. The ylides are converted to electron-poor alkenes via elimination of TPP in solvent-free conditions. Almost all of the final products are valuable families of compounds. †Dedicated to Professor Issa Yavari on the occasion of his 59th birthday.

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Section: Reaction Of Triphenylphosphine Dialkyl Acetylenedicarboxylamentioning

confidence: 99%

“…After 1953 the chemistry of phosphorus ylides progressed intensively. Outstanding achievement in the development of phosphorus ylide chemistry was contributed by Bestmann [20,21], Corey [22], Schlosser [23], Trippett [24], Seyferth [25], and many other chemists.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactions of Stabilized Phosphorus Ylides

Ramazani

Kazemizadeh

Ahmadi³

et al. 2008

COC

106

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“…[8h] In the case of thorium, Liddle has synthesized at horium carbene complex with Th À Cdistances from 2.41-2.51 . [12] Herein, we report two new phosphorano-stabilized carbene complexes with short, 2.299(6) and 2.3137 (18) ,t horiumcarbon distances. [12] Herein, we report two new phosphorano-stabilized carbene complexes with short, 2.299(6) and 2.3137 (18) ,t horiumcarbon distances.…”

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confidence: 94%

Formation of Methane versus Benzene in the Reactions of (C₅Me₅)₂Th(CH₃)₂ with [CH₃PPh₃]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes

et al. 2017

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The reaction of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with the phosphonium salts [CH 3 PPh 3 ]X (X = Cl, Br,I )w as investigated. When X = Br and I, two equivalents of methane are liberated to afford( C 5 Me 5 ) 2 Th[CHPPh 3 ]X, rare terminal phosphoranostabilized carbenes with thorium. These complexes feature the shortest thorium-carbon bonds ( % 2.30 )r eported to date, and electronic structure calculations shows ome degree of multiple bonding.However,when X = Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate,yielding (C 5 Me 5 ) 2 Th-[k 2 -(C,C')-(CH 2 )(CH 2 )PPh 2 ]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH 3 PPh 3 ]X, X = Cl and Is howed that in the case of iodide, thermodynamics prevents the production of benzenea nd favors formation of the carbene.

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“…It was very soon shown that this reaction is generally applicable, and that high selectivity and proceeds without rearrangement and isomerization. After 1953 the chemistry of phosphorus ylides progressed intensively [32][33][34][35][36][37][38].…”

Section: Introductionmentioning

confidence: 99%

“…These cyclobutene derivatives undergo electrocyclic ring-opening reactions in boiling toluene to produce highly electron-deficient 1,3-dienes (35) (Scheme 11) [64]. 2-Acetylbutyrolactone (36) undergoes a smooth reaction with TPP (1) and DAAD (2) to produce stabilized diastereomeric phosphorus ylides (37). Compounds (37) possess two stereogenic centers, and two diastereomers are expected.…”

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confidence: 99%

Preparation of Stabilized Phosphorus Ylides via Multicomponent Reactions and Their Synthetic Applications

Ramazani

Kazemizadeh

2011

COC

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Triphenylphosphine (TPP), dialkyl acetylenedicarboxylates (DAAD), and acids such as phenols, imides, amides, enols, oximes and alcohols react with each other via a multicomponent reaction to produce stabilized phosphorus ylides. The reactions take place easily, through formation of intermediate formed by the Michael addition of the triphenylphosphine to dialkyl acetylenedicarboxylates and concomitant protonation of the intermediate by an acid leads to vinyltriphenylphosphonium salts. The salts are unstable intermediates and undergo a subsequent Michael addition leads to stabilized phosphorus ylides. In some cases ylide products are stable, but in other cases they cannot be isolated and appear to occur as intermediates on the pathway to an observed product. The stabilized phosphorus ylides are able to take part in the normal intramolecular Wittig reactions and produce a variety of heterocyclic or carbocyclic compounds, but they are not able to participate in the intermolecular Wittig reactions.

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Studies in Phosphinemethylene Chemistry. X. The Reaction of Organolithium Reagents with Alkyltriphenylphosphonium Halides. The Mechanism of Phosphinemethylene Formation¹

Cited by 38 publications

References 0 publications

Synthesis and Reactions of Stabilized Phosphorus Ylides

Synthesis and Reactions of Stabilized Phosphorus Ylides

Formation of Methane versus Benzene in the Reactions of (C₅Me₅)₂Th(CH₃)₂ with [CH₃PPh₃]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes

Preparation of Stabilized Phosphorus Ylides via Multicomponent Reactions and Their Synthetic Applications

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Studies in Phosphinemethylene Chemistry. X. The Reaction of Organolithium Reagents with Alkyltriphenylphosphonium Halides. The Mechanism of Phosphinemethylene Formation1

Cited by 38 publications

References 0 publications

Synthesis and Reactions of Stabilized Phosphorus Ylides

Synthesis and Reactions of Stabilized Phosphorus Ylides

Formation of Methane versus Benzene in the Reactions of (C5Me5)2Th(CH3)2 with [CH3PPh3]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes

Preparation of Stabilized Phosphorus Ylides via Multicomponent Reactions and Their Synthetic Applications

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Studies in Phosphinemethylene Chemistry. X. The Reaction of Organolithium Reagents with Alkyltriphenylphosphonium Halides. The Mechanism of Phosphinemethylene Formation¹

Formation of Methane versus Benzene in the Reactions of (C₅Me₅)₂Th(CH₃)₂ with [CH₃PPh₃]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes