Ruthenium-catalyzed cis-dihydroxylation of alkenes: Scope and limitations

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

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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

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Keywords

  • Alkenes
  • Catalysis
  • Dihydroxylations
  • Electrophilicity
  • Ruthenium compounds

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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