Ruthenium-catalyzed cis-dihydroxylation of alkenes

Scope and limitations

Tony Kung Ming Shing, Eric K.W. Tam, Vincent W.F. Tai, Ivan H.F. Chung, Qin Jiang

Research output: Contribution to journalArticle

150 Citations (Scopus)

Abstract

Oxidative ruthenium catalysis (0.07 molequiv RuCl3· (H2O)3, 1.5 molequiv NaIO4, EtOAc/CH 3CN/H2O 3:3:1), beyond the usual C-C bond cleavage to give dicarbonyls, has been shown to syn-dihydroxylate a wide range of alkenes (except for strained bicyclic alkenes, sterically hindered trisubstituted alkenes, and most tetrasubstituted alkenes) to give vicinal diols rapidly (within minutes) and efficiently. The minor products are the usual oxidative fission products, namely, ketones and aldehydes or carboxylic acids, and sometimes ketols. Longer reaction times lower the yields of most diols, probably owing to oxidative glycol cleavage. Reactions with substrates containing one or more electron-with-drawing groups in conjugation with or adjacent to the alkene moiety are generally slower but give better yields. The diastereoselectivity of the present "flash" dihydroxylation, anti to the existing α-stereogenic center, with cycloalkenes is excellent whereas that with acyclic alkenes is moderate to poor. Sodium metaperio-date is still the best co-oxidant for the catalytic reaction. Aqueous acetonitrile (approximately 86%) as an alternative solvent system was found to give better yields of 1,2-diols than the original solvent system in some cases.

Original languageEnglish
Pages (from-to)50-57
Number of pages8
JournalChemistry - A European Journal
Volume2
Issue number1
DOIs
Publication statusPublished - 1996 Dec 1
Externally publishedYes

Fingerprint

Ruthenium
Alkenes
Olefins
Cycloparaffins
Glycols
Fission products
Carboxylic Acids
Ketones
Aldehydes
Acetonitrile
Carboxylic acids
Oxidants
Catalysis
Sodium
Electrons
Substrates

Keywords

  • Alkenes
  • Catalysis
  • Dihydroxylations
  • Electrophilicity
  • Ruthenium compounds

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Shing, T. K. M., Tam, E. K. W., Tai, V. W. F., Chung, I. H. F., & Jiang, Q. (1996). Ruthenium-catalyzed cis-dihydroxylation of alkenes: Scope and limitations. Chemistry - A European Journal, 2(1), 50-57. https://doi.org/10.1002/chem.19960020111

Ruthenium-catalyzed cis-dihydroxylation of alkenes : Scope and limitations. / Shing, Tony Kung Ming; Tam, Eric K.W.; Tai, Vincent W.F.; Chung, Ivan H.F.; Jiang, Qin.

In: Chemistry - A European Journal, Vol. 2, No. 1, 01.12.1996, p. 50-57.

Research output: Contribution to journalArticle

Shing, Tony Kung Ming ; Tam, Eric K.W. ; Tai, Vincent W.F. ; Chung, Ivan H.F. ; Jiang, Qin. / Ruthenium-catalyzed cis-dihydroxylation of alkenes : Scope and limitations. In: Chemistry - A European Journal. 1996 ; Vol. 2, No. 1. pp. 50-57.
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