Oxygen transfer from sulfoxides

Selective oxidation of alcohols catalyzed by polyoxomolybdates

Alexander M. Khenkin, Ronny Neumann

Research output: Contribution to journalArticle

57 Citations (Scopus)

Abstract

Benzylic, allylic, and aliphatic alcohols are oxidized to aldehydes and ketones in a reaction catalyzed by Keggin-type polyoxomolybdates, PVxMo(12-x)O40 -(3+x) (x = 0, 2), with DMSO as a solvent. The oxidation of benzylic alcohols is quantitative within hours and selective, whereas that of allylic alcohols is less selective. Oxidation of aliphatic alcohols is slower but selective. Further mechanistic studies revealed that, for H3PMo12O40 as a catalyst and benzylic alcohols as substrates, the sulfoxide is in fact an oxygen donor in the reaction. Postulated reaction steps as determined from isotopelabeling experiments, kinetic isotope effects, and Hammett plots include (a) sulfoxide activation by complexation to the polyoxometalate and (b) oxygen transfer from the activated sulfoxide and elimination of water from the alcohol. The mechanism is supported by the reaction kinetics.

Original languageEnglish
Pages (from-to)7075-7079
Number of pages5
JournalJournal of Organic Chemistry
Volume67
Issue number20
DOIs
Publication statusPublished - Oct 4 2002

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sulfoxide
Sulfoxides
Alcohols
Oxygen
Oxidation
Dimethyl Sulfoxide
Ketones
Complexation
Aldehydes
Reaction kinetics
Isotopes
Chemical activation
Catalysts
Kinetics
Water
Substrates
Experiments

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Oxygen transfer from sulfoxides : Selective oxidation of alcohols catalyzed by polyoxomolybdates. / Khenkin, Alexander M.; Neumann, Ronny.

In: Journal of Organic Chemistry, Vol. 67, No. 20, 04.10.2002, p. 7075-7079.

Research output: Contribution to journalArticle

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