Oxygenation of Methylarenes to Benzaldehyde Derivatives by a Polyoxometalate Mediated Electron Transfer-Oxygen Transfer Reaction in Aqueous Sulfuric Acid

Bidyut Bikash Sarma, Irena Efremenko, Ronny Neumann

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The synthesis of benzaldehyde derivatives by oxygenation of methylarenes is of significant conceptual and practical interest because these compounds are important chemical intermediates whose synthesis is still carried out by nonsustainable methods with very low atom economy and formation of copious amounts of waste. Now an oxygenation reaction with a 100% theoretical atom economy using a polyoxometalate oxygen donor has been found. The product yield is typically above 95% with no "overoxidation" to benzoic acids; H2 is released by electrolysis, enabling additional reaction cycles. An electrocatalytic cycle is also feasible. This reaction is possible through the use of an aqueous sulfuric acid solvent, in an aqueous biphasic reaction mode that also allows simple catalyst recycling and recovery. The solvent plays a key role in the reaction mechanism by protonating the polyoxometalate thereby enabling the activation of the methylarenes by an electron transfer process. After additional proton transfer and oxygen transfer steps, benzylic alcohols are formed that further react by an electron transfer-proton transfer sequence forming benzaldehyde derivatives. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)5916-5922
Number of pages7
JournalJournal of the American Chemical Society
Volume137
Issue number18
DOIs
Publication statusPublished - May 13 2015

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Proton transfer
Oxygenation
Sulfuric acid
Protons
Electrons
Oxygen
Electrolysis
Derivatives
Atoms
Benzoic acid
Benzoates
Recycling
Alcohols
Chemical activation
Recovery
Catalysts
sulfuric acid
benzaldehyde
polyoxometalate I

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Oxygenation of Methylarenes to Benzaldehyde Derivatives by a Polyoxometalate Mediated Electron Transfer-Oxygen Transfer Reaction in Aqueous Sulfuric Acid. / Sarma, Bidyut Bikash; Efremenko, Irena; Neumann, Ronny.

In: Journal of the American Chemical Society, Vol. 137, No. 18, 13.05.2015, p. 5916-5922.

Research output: Contribution to journalArticle

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AB - The synthesis of benzaldehyde derivatives by oxygenation of methylarenes is of significant conceptual and practical interest because these compounds are important chemical intermediates whose synthesis is still carried out by nonsustainable methods with very low atom economy and formation of copious amounts of waste. Now an oxygenation reaction with a 100% theoretical atom economy using a polyoxometalate oxygen donor has been found. The product yield is typically above 95% with no "overoxidation" to benzoic acids; H2 is released by electrolysis, enabling additional reaction cycles. An electrocatalytic cycle is also feasible. This reaction is possible through the use of an aqueous sulfuric acid solvent, in an aqueous biphasic reaction mode that also allows simple catalyst recycling and recovery. The solvent plays a key role in the reaction mechanism by protonating the polyoxometalate thereby enabling the activation of the methylarenes by an electron transfer process. After additional proton transfer and oxygen transfer steps, benzylic alcohols are formed that further react by an electron transfer-proton transfer sequence forming benzaldehyde derivatives. (Chemical Equation Presented).

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