Carbohydrate-Substituted Triarylphosphanes— A New Class of Ligands for Two-Phase Catalysis

Beller, Matthias; Krauter, Jürgen G.E.; Zapf, Alexander

doi:10.1002/anie.199707721

Cited by 101 publications

(51 citation statements)

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“…The simple catalyst separation is an important step towards the development of environmentally friendly industrial processes. There is a wide variety of literature on Mizoroki-Heck reactions with TPPTS or related water-soluble phosphine salts 55-63 ( Figure 15.5) in aqueous organic solvents [156][157][158][159][160][161][162][163][164][165][166][167][168][169][170][171][172]. Ligand 56 was tested in various Mizoroki-Heck couplings and compared with a few other water-soluble ligands.…”

Section: Aqueous Systems With Additional Organic Solventmentioning

confidence: 99%

Mizoroki–Heck Reactions: Modern Solvent Systems and Reaction Techniques

Bonrath¹,

Létinois²,

Netscher³

et al. 2009

The Mizoroki–Heck Reaction

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Section: Aqueous Systems With Additional Organic Solventmentioning

confidence: 99%

Mizoroki–Heck Reactions: Modern Solvent Systems and Reaction Techniques

Bonrath¹,

Létinois²,

Netscher³

et al. 2009

The Mizoroki–Heck Reaction

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“…These hydrophilic carbohydrate-substituted triarylphosphines, in combination with Pd(OAc) 2 (ligand:Pd = 3:1), gave better results than the catalyst system composed of a 3:1 mixture of TPPTS (68) and Pd(OAc) 2 in cross-coupling reactions of aryl bromides with phenylboronic acid in ethanol-water-di-n-butylether (2:3:1) or in ethanolwater-toluene at 78°C in the presence of Na 2 CO 3 . 125 (71) is another water-soluble phosphine ligand which was synthesised to perform efficient palladium-catalysed reactions of aryl halides with arylboronic acids in water. 126 Interestingly, the catalyst precursor prepared from 71 and PdCl 2 (1,5-cyclooctadiene) in acetonitrile revealed higher activity than that synthesised from the water-soluble ligands 67 or 68.…”

Section: Water-soluble Pd Catalyst Systemsmentioning

confidence: 99%

Untitled

2004

Synthesis

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This review with 206 references covers the literature published until March 2004 on the development and applications of new efficient catalyst systems for the Suzuki palladium-catalysed cross-coupling reaction of organoboron compounds with organic electrophiles. Where possible, the relative advantages of the new catalyst systems in this synthetically very important carbon-carbon bond forming reaction have been compared.

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“…Recovery is easy in the case of the ligandless Heck reactions as the catalyst precipitates completely once all the substrate has been used up. If ligands are used this can be a problem, though sometimes water-soluble ligands can be used to allow for two-phase catalysis (50)(51)(52)(53). Ionic liquids have also been reported as an aid in catalyst recycle (54)(55)(56).…”

Section: Development Aspectsmentioning

confidence: 99%

The Heck reaction in the production of fine chemicals

2001

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Abstract. An overview is given of the use of the Heck reaction for the production of fine chemicals. Five commercial products have been identified that are produced on a scale in excess of 1 ton/year. The herbicide Prosulfuron™ is produced via a Matsuda reaction of 2-sulfonatobenzenediazonium on 3,3,3-trifluoropropene. The sunscreen agent 2-ethylhexyl p-methoxy-cinnamate has been produced on pilot scale using Pd/C as catalyst. Naproxen™ is produced via the Heck reaction of 2-bromo-6-methoxy-naphthalene on ethylene, followed by carbonylation of the product. Monomers for coatings are produced via a Heck reaction on 2-bromo-benzocyclobutene. A key step in the production of the antiasthma agent Singulair™ is the use of the Heck reaction of methyl 2-iodo-benzoate on allylic alcohol (18) to give ketone (20). The high cost of palladium has spurred much research aimed at the development of more active palladium catalysts. Ligandless catalysts are very attractive for production, but work only on reactive substrates. Palladacycles are much more stable than Pd-phosphine complexes and can be used at higher temperatures. The same effect has been reached with pincer ligands. Bulky ligands lead to coordinatively unsaturated Pd-complexes, which are highly active for the Heck reaction. Recycle of palladium catalysts is also very important to reduce cost. Immobilization of catalysts by attaching ligands to solid support is not very useful, because of leaching and reduced activity. In ligandless Heck reactions the catalyst can be precipitated on carriers such as silica, dicalite, or celite. This material can be restored to its original activity by treatment with I 2 or Br 2 .Key words: homogeneous catalysis, palladium, arylation, olefination, ligandless, catalyst recycle.Résumé : On présente une revue de l'utilisation de la réaction de Heck dans la production de produits chimiques fins. On a identifié cinq produits commerciaux qui sont produits sur une échelle supérieure à une tonne par année. L'herbicide Prosulfuron ® est produit par le biais d'une réaction de Matsuda du 2-sulfonatobenzènediazonium sur le 3,3,3-trifluoropropène. L'agent solaire 4-méthoxycinnamate de 2-éthylhexyle a été produit à l'échelle pilote à l'aide d'un catalyseur de Pd/C. Le Naproxen ® est produit par le biais d'une réaction de Heck du 2-bormo-6-méthoxynaphtalène sur l'éthylène, suivie d'une carbonylation du produit. Des monomères de couches protectrices sont produits par le biais d'une réaction de Heck sur le 2-bromobenzocyclobutène. Une étape clé dans la production de l'agent antiasthmatique Singulair ® est l'utilisation de la réaction de Heck du 2-iodobenzoate de méthyle sur l'alcool allylique 18 pour obtenir la cétone 20. Le prix élevé du palladium a provoqué beaucoup de recherches dans le but de dé-velopper des catalyseurs du palladium qui soient plus actifs. Les catalyseurs sans ligands sont très attrayants pour la production, mais ils ne sont utiles qu'avec des substrats réactifs. Les cycles palladiés sont beaucoup plus stables que les complexes Pd/...

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Carbohydrate-Substituted Triarylphosphanes— A New Class of Ligands for Two-Phase Catalysis

Cited by 101 publications

References 0 publications

Mizoroki–Heck Reactions: Modern Solvent Systems and Reaction Techniques

Mizoroki–Heck Reactions: Modern Solvent Systems and Reaction Techniques

Untitled

The Heck reaction in the production of fine chemicals

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