Tetraarylphosphonium Salts as Solubility‐Control Groups: Phosphonium‐Supported Triphenylphosphine and Azodicarboxylate Reagents

Poupon, Jean‐Christophe; Boezio, Alessandro A.; Charette, André B.

doi:10.1002/anie.200503599

Cited by 47 publications

(32 citation statements)

References 82 publications

(11 reference statements)

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“…The process was devised starting from commercially available 1,3-dibromobenzene which was converted into the key precursor e 3-(bromophenyl)diphenylphosphine sulfide via monophosphorylation with Ph 2 PCl followed by in situ addition of elemental sulfur to the corresponding phosphine (Scheme 2) [12]. The sequential treatment of monothiophosphorylated bromide with n-BuLi and N-vinyl pyrrolidone, N-(diethoxymethyl)valerolactam or N-vinyl caprolactam led to the formation of the target ligands with five-, six-, and seven-membered azacycloalkene moiety, isolated as viscous yellowish oils in moderate yields (38e61%) after chromatography purification.…”

Section: Synthesis Of Ligands and Complexesmentioning

confidence: 99%

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Hybrid NCS palladium pincer complexes of thiophosphorylated benzaldimines and their ketimine analogs

Aleksanyan

Козлов

Shevchenko

et al. 2012

Journal of Organometallic Chemistry

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Section: Synthesis Of Ligands and Complexesmentioning

confidence: 99%

“…To a solution of (3-bromophenyl)diphenylphosphine, prepared according to the literature procedure [12] from 1,3-dibromobenzene (5.4 g, 23 mmol), n-BuLi (1.6 M in hexane, 15 mL, 24 mmol), and Ph 2 PCl (4. 8 g, 22 mmol), in 30 mL of THF at À50 C, sulfur (0.…”

Section: Synthesis Of (3-bromophenyl)(diphenyl)phosphine Sulfidementioning

confidence: 99%

Hybrid NCS palladium pincer complexes of thiophosphorylated benzaldimines and their ketimine analogs

Aleksanyan

Козлов

Shevchenko

et al. 2012

Journal of Organometallic Chemistry

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“…[10,11] Recently, we reported that the tetraarylphosphonium (TAP) unit can be used as a solubility control group to modify and predict the solubility properties of supported reagents and synthetic intermediates. A number of TAP-supported reagents derived from triphenylphosphine, diethyl azodicarboxylate, [12] tributyltin chloride, [13] and dialkylcarbodiimide [14] have been prepared and successfully used in various reactions. Furthermore, the reagents by-products can be removed from the reaction medium by a precipitation/ filtration sequence.…”

Section: Introductionmentioning

confidence: 99%

Nickel‐Catalyzed Synthesis of Phosphonium Salts from Aryl Halides and Triphenylphosphine

Marcoux

Charette

2008

Adv Synth Catal

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An efficient method to synthesize functionalized tetraarylphosphonium salts is described. The nickel-catalyzed coupling reaction between aryl iodides, bromides, chlorides, or triflates and triphenylphosphine generates tetraarylphosphonium salts in high yields. The coupling is wide in scope and tolerates a variety of functional groups such as alcohols, amides, ketones, aldehydes, phenols, phosphines and amines.

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“…These modifications of the original oxidant or reductant are considered to intend a separation-free or separation-friendly process. 4,5 Formation of triphenylphosphane oxide is practically insignificant matter in the separation process due to its facile crystallization in non-polar solvents. In contrast, separation of the other co-product, diethyl or diisopropyl hydrazinedicarboxylate requires highly capable column chromatography to isolate a target compound.…”

mentioning

confidence: 99%

Di-2-methoxyethyl Azodicarboxylate (DMEAD): An Inexpensive and Separation-friendly Alternative Reagent for the Mitsunobu Reaction

Sügimura¹,

Hagiya²

2007

Chemistry Letters

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Di-2-methoxyethyl azodicarboxylate (DMEAD) was prepared as an alternative of DEAD or DIAD for the Mitsunobu reaction. Removal of the hydrazinedicarboxylate generated from DMEAD becomes much easier owing to the polar and water-soluble property.The Mitsunobu reaction is popular in organic synthesis to introduce an acidic nucleophile (carboxylic acid, phenol, imide, etc.) to an alcoholic function under mild conditions.2 The notable property of this reaction is complete inversion of stereochemistry at the alcoholic function. The original procedure consists of mixing an alcohol and a nucleophile with diethyl azodicarboxylate (DEAD) and triphenylphosphane at ambient temperature.3 This oxidant-reductant combination to cause dehydration in the Mitsunobu reaction is still widely used although diisopropyl azodicarboxylate (DIAD) is also conveniently employed as a more stable analogue of DEAD. A major drawback of this process is formation of two co-products, hydrazinedicarboxylate and phosphane oxide, which must be removed from the reaction mixture to isolate a target compound. Many efforts have been undertaken to solve this issue: e.g., one of the reagents is supported by polymer or solid to perform the separation by filtration, or is attached to an acidic, basic, or fluorous function to allow the separation by extraction into a basic or acidic aqueous layer or into fluorous solvent. These modifications of the original oxidant or reductant are considered to intend a separation-free or separation-friendly process. 4,5 Formation of triphenylphosphane oxide is practically insignificant matter in the separation process due to its facile crystallization in non-polar solvents. In contrast, separation of the other co-product, diethyl or diisopropyl hydrazinedicarboxylate requires highly capable column chromatography to isolate a target compound. One also often faces a problem that several side products of the hydrazinedicarboxylate cannot be removed completely from the product. In situ recycling of DEAD that makes it a catalyst is one of the solutions. 6 Total removal of the hydrazinedicarboxylate and the side-products can be performed by polymerization of norbornene units incorporated in the reagent as to be called impurity annihilation.7 Very recently, di-4-chlorobenzyl analogue was reported, 8 where the hydrazinedicarboxylate can be removed by the crystallization. We have made another approach to this issue by molecular design to enable the separation of a hydrazinedicarboxylate by extraction with neutral water. The preparation cost and handling were also considered to compete with DEAD and DIAD in the commercial source. Di-2-methoxyethyl azodicarboxylate (DMEAD) is a new reagent, which will be detailed in this report.Di-2-dimethoxyethyl hydrazinedicarboxylate (1) was prepared by mixing hydrazine hydrate and 2-methoxyethyl chloroformate in ethanol in the presence of sodium carbonate (72% yield after recrystallization, Scheme 1).9,10 Solubility of 1 is good in chloroform (0.25 g/mL) and ethyl acetate (0.1), but very poor (<0...

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Tetraarylphosphonium Salts as Solubility‐Control Groups: Phosphonium‐Supported Triphenylphosphine and Azodicarboxylate Reagents

Abstract: Tremendous effort has been invested over the last few decades to develop novel supports to facilitate organic synthesis. These supports have been used not only to carry out multistep syntheses, [1] but also to bind catalysts, reagents,

Cited by 47 publications

References 82 publications

Hybrid NCS palladium pincer complexes of thiophosphorylated benzaldimines and their ketimine analogs

Hybrid NCS palladium pincer complexes of thiophosphorylated benzaldimines and their ketimine analogs

Nickel‐Catalyzed Synthesis of Phosphonium Salts from Aryl Halides and Triphenylphosphine

Di-2-methoxyethyl Azodicarboxylate (DMEAD): An Inexpensive and Separation-friendly Alternative Reagent for the Mitsunobu Reaction

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