Aqueous biphasic oxidation: A water-soluble polyoxometalate catalyst for selective oxidation of various functional groups with hydrogen peroxide

Dorit Sloboda-Rozner, Peter Witte, Paul L. Alsters, Ronny Neumann

Research output: Contribution to journalArticle

106 Citations (Scopus)

Abstract

A "sandwich" type polyoxometalate, Na12[(WZn 3(H2O)2][(ZnW9O34) 2], was used as an oxidation catalyst in aqueous biphasic reaction media to effect oxidation of alcohols, diols, pyridine derivatives, amines and aniline derivatives with hydrogen peroxide. The catalyst was shown by 183W NMR to be stable in aqueous solutions in the presence of H 2O2 and showed only minimal non-productive decomposition of the oxidant. Secondary alcohols were selectively oxidized to ketones, while primary alcohols tended to be oxidized to the corresponding carboxylic acids, although secondary alcohols were selectively oxidized in the presence of primary alcohols. Vicinal diols yielded carbon-carbon bond cleavage products in very high yields. Pyridine derivatives were oxidized to the respective TV-oxides, but strongly electron-withdrawing moieties inhibited the oxidation reaction. Primary amines were oxidized to the oximes, but significantly hydrolyzed in situ. Aniline derivatives were oxidized to the corresponding azoxy or nitro products depending on the substitution pattern in the aromatic ring. Catalyst recovery and recycle was demonstrated.

Original languageEnglish
Pages (from-to)339-345
Number of pages7
JournalAdvanced Synthesis and Catalysis
Volume346
Issue number2-3
Publication statusPublished - Feb 2004

Fingerprint

Hydrogen peroxide
Hydrogen Peroxide
Functional groups
Alcohols
Oxidation
Catalysts
Water
Derivatives
Aniline
Pyridine
Amines
Carbon
Oximes
Carboxylic Acids
Ketones
Carboxylic acids
Oxidants
Oxides
Substitution reactions
Nuclear magnetic resonance

Keywords

  • Alcohols
  • Biphasic reactions
  • Homogeneous catalysis, hydrogen peroxide
  • Oxidation
  • Polyoxometalates

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Organic Chemistry
  • Catalysis

Cite this

Aqueous biphasic oxidation : A water-soluble polyoxometalate catalyst for selective oxidation of various functional groups with hydrogen peroxide. / Sloboda-Rozner, Dorit; Witte, Peter; Alsters, Paul L.; Neumann, Ronny.

In: Advanced Synthesis and Catalysis, Vol. 346, No. 2-3, 02.2004, p. 339-345.

Research output: Contribution to journalArticle

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N2 - A "sandwich" type polyoxometalate, Na12[(WZn 3(H2O)2][(ZnW9O34) 2], was used as an oxidation catalyst in aqueous biphasic reaction media to effect oxidation of alcohols, diols, pyridine derivatives, amines and aniline derivatives with hydrogen peroxide. The catalyst was shown by 183W NMR to be stable in aqueous solutions in the presence of H 2O2 and showed only minimal non-productive decomposition of the oxidant. Secondary alcohols were selectively oxidized to ketones, while primary alcohols tended to be oxidized to the corresponding carboxylic acids, although secondary alcohols were selectively oxidized in the presence of primary alcohols. Vicinal diols yielded carbon-carbon bond cleavage products in very high yields. Pyridine derivatives were oxidized to the respective TV-oxides, but strongly electron-withdrawing moieties inhibited the oxidation reaction. Primary amines were oxidized to the oximes, but significantly hydrolyzed in situ. Aniline derivatives were oxidized to the corresponding azoxy or nitro products depending on the substitution pattern in the aromatic ring. Catalyst recovery and recycle was demonstrated.

AB - A "sandwich" type polyoxometalate, Na12[(WZn 3(H2O)2][(ZnW9O34) 2], was used as an oxidation catalyst in aqueous biphasic reaction media to effect oxidation of alcohols, diols, pyridine derivatives, amines and aniline derivatives with hydrogen peroxide. The catalyst was shown by 183W NMR to be stable in aqueous solutions in the presence of H 2O2 and showed only minimal non-productive decomposition of the oxidant. Secondary alcohols were selectively oxidized to ketones, while primary alcohols tended to be oxidized to the corresponding carboxylic acids, although secondary alcohols were selectively oxidized in the presence of primary alcohols. Vicinal diols yielded carbon-carbon bond cleavage products in very high yields. Pyridine derivatives were oxidized to the respective TV-oxides, but strongly electron-withdrawing moieties inhibited the oxidation reaction. Primary amines were oxidized to the oximes, but significantly hydrolyzed in situ. Aniline derivatives were oxidized to the corresponding azoxy or nitro products depending on the substitution pattern in the aromatic ring. Catalyst recovery and recycle was demonstrated.

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