Synthetic Transformations of Vinyl and Aryl Triflates

Ritter, Kurt

doi:10.1055/s-1993-25931

Cited by 449 publications

(221 citation statements)

References 0 publications

Supporting

Mentioning

218

Contrasting

Unclassified

Order By: Relevance

“…Initially, reports only mentioned the use of aryl bromides and iodides as arylating agent. Later, variants were developed using aromatic triflates (11), aroyl chlorides (12), aryl sulfonyl chlorides (13), aromatic diazonium salts (14) (the Matsuda reaction), aroyl anhydrides (15), aryl chlorides (16)(17)(18)(19)(20), and arylsilanols (21). Consequently, the number of commercially available aromatic substrates is very high.…”

Section: The Heck Reactionmentioning

confidence: 99%

The Heck reaction in the production of fine chemicals

2001

View full text Add to dashboard Cite

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/...

show abstract

Section: The Heck Reactionmentioning

confidence: 99%

The Heck reaction in the production of fine chemicals

2001

View full text Add to dashboard Cite

show abstract

“…There are two broad approaches for the synthesis of 4-substituted benzopyrans. The first approach 18,25 deals with the opening of an epoxide at the 3,4-double bond of the benzopyran nucleus (Scheme 1a) by nucleophilic attack of electron rich heterocycles in the presence of base and dehydration to afford 4-substituted chromenes. …”

Section: Introductionmentioning

confidence: 99%

Facile synthesis of various 2-substituted-4-(2-pyridyl) benzopyran analogues as target potassium channel opener

Tripathi¹,

Mukherjee²,

Koul³

et al. 2010

Arkivoc

View full text Add to dashboard Cite

show abstract

“…Vinyl triflates are important building blocks in organic synthesis, [1] especially as intermediates for C-C bond formation by Pd-catalyzed coupling reactions. [1][2] Vinyl fluorosulfonates have also been used as precursors for such coupling reactions, although to a much less extent.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2] Vinyl fluorosulfonates have also been used as precursors for such coupling reactions, although to a much less extent. [3] Surprisingly enough, only two routes are used to prepare these important intermediates and they are mainly obtained from ketones.…”

Section: Introductionmentioning

confidence: 99%

One‐Step Addition of Sulfonic Acids to Acetylene Derivatives: An Alternative and Stereoselective Approach to Vinyl Triflates and Fluorosulfonates

et al. 2007

View full text Add to dashboard Cite

Acetylenic acids and esters as well as acetylenic ketones were efficiently and stereoselectively converted in one step to the corresponding vinyl triflates or fluorosulfonates in triflic or fluorosulfonic acids. Depending on the reaction conditions the E or the Z isomer can be obtained very conveniently in high isolated yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

show abstract

Synthetic Transformations of Vinyl and Aryl Triflates

Cited by 449 publications

References 0 publications

The Heck reaction in the production of fine chemicals

The Heck reaction in the production of fine chemicals

Facile synthesis of various 2-substituted-4-(2-pyridyl) benzopyran analogues as target potassium channel opener

One‐Step Addition of Sulfonic Acids to Acetylene Derivatives: An Alternative and Stereoselective Approach to Vinyl Triflates and Fluorosulfonates

Contact Info

Product

Resources

About