Multiple use of Palladium in a homogeneous and a consecutive heterogeneous catalytic reaction

Baumeister, P.; Meyer, Wolfgang; Oertle, Konrad; Seifert, G.; Siegrist, Urs; Steiner, Heinz

doi:10.1016/s0167-2991(97)80885-3

Cited by 24 publications

(23 citation statements)

References 3 publications

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“…A very convincing demonstration of the powerfulness of the HM reaction was carried out at the former Ciba Geigy AG Company using a unique internal arenediazonium sulfonate salt to prepare herbicide Prosulfuron (Scheme 26). [81] Arylation of 3,3,3-trifluoropropene using Pd 2 (dba) 3 as catalyst and immediate hydrogenation by adding active carbon to the already present Pd 0 furnished the requisite intermediate for the synthesis of this sulfonyl urea based agrochemical. In spite of the fact that a diazotization step is present, only 2 kg of waste is produced per kg of product.…”

Section: Total and Formal Synthesesmentioning

confidence: 99%

Evolution and Synthetic Applications of the Heck–Matsuda Reaction: The Return of Arenediazonium Salts to Prominence

2011

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This review highlights the potential and the versatility of arenediazonium salts as viable alternatives to conventional aryl halides and oxygen-based electrophiles for Pd-catalyzed Heck reactions. It also presents an overview of the field over the last decade, including some historical perspective of the Heck-Matsuda (HM) reaction with general considerations regarding reaction conditions, type of catalysts used, and the application of arenediazonium salts as reagents for the HM arylation of several types of alkenes. Throughout this review, the principal aspects related to reactivity and selectivity are discussed, and when applicable a comparison is made between the HM and the conventional Heck reactions. Onepot procedures that involve generation of the arenediazonium salt in situ from the corresponding aniline have been

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Section: Total and Formal Synthesesmentioning

confidence: 99%

Evolution and Synthetic Applications of the Heck–Matsuda Reaction: The Return of Arenediazonium Salts to Prominence

2011

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“…Matsuda-Heck Reaction [7] This case history is somewhat special since catalysis was not only used for production purposes but already as a tool during product discovery. At the same time as the just published Pd-catalyzed reaction of olefins with aryldiazonium salts [19] (a variant of the Heck [18] reaction) was investigated at the Central Research Laboratories of Ciba-Geigy, its Agro Research Department was interested in new sulfonylurea herbicides (see Figure 15).…”

Section: Building Block For a New Herbicide Via Thementioning

confidence: 99%

“…Investigations of the Heck reaction: acid chlorides as starting materials; high performance catalysts; Heck-Matsuda reaction for product discovery; [7,8,9] ca. 1985 Development of first industrial processes (selected milestones see below) [7,10] 1995 Ni catalysts for Suzuki coupling developed [11] 1998 Catalysts for the activation of aryl chlorides for Heck, Suzuki, Buchwald-Hartwig amination etc.…”

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confidence: 99%

“…1985 Development of first industrial processes (selected milestones see below) [7,10] 1995 Ni catalysts for Suzuki coupling developed [11] 1998 Catalysts for the activation of aryl chlorides for Heck, Suzuki, Buchwald-Hartwig amination etc. ; secondary phosphines; palladacycles -secondary phosphines [13,14] 1998 Systematic investigation of the carbonylation of aryl halides; carbonylation of (hetero) aryl chlorides [10,15] When discussing absolute figures, one should always keep in mind that these can vary broadly depending on the situation for a specific process development.…”

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confidence: 99%

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Industrial R&D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results

Blaser¹,

Indolese²,

Naud³

et al. 2004

Adv Synth Catal

217

103

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R&D issues for the application of Pd-and Ni-catalyzed C À C and C À N coupling reactions in the fine chemicals industry are discussed. In a first part, some background is given on industrial R&D and the role of C À C and C À N coupling for preparative applications is described. The following principal approaches to industrial research are illustrated with relevant examples from the literature and from our own laboratories: i) development of catalysts and catalytic methodologies with industrial potential; ii) finding shorter routes to target molecules using catalytic methods; iii) development of industrial catalytic processes in multi-step syntheses.

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“…The first reported example of industrial use of the Heck reaction was for the production of Prosulfuron™, a new and highly active herbicide, by Ciba-Geigy (now Novartis) (33). In this instance, the Matsuda variant was used to great advantage as the substrate also contains a sulfonate group.…”

Section: The Herbicide Prosulfuron™mentioning

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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Multiple use of Palladium in a homogeneous and a consecutive heterogeneous catalytic reaction

Cited by 24 publications

References 3 publications

Evolution and Synthetic Applications of the Heck–Matsuda Reaction: The Return of Arenediazonium Salts to Prominence

Evolution and Synthetic Applications of the Heck–Matsuda Reaction: The Return of Arenediazonium Salts to Prominence

Industrial R&D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results

The Heck reaction in the production of fine chemicals

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