Mechanistic insights into the malonoyl peroxide syn-dihydroxylation of alkenes

Michael J. Rawling, Julian H. Rowley, Matthew Campbell, Alan R. Kennedy, John A. Parkinson, Nicholas C. O. Tomkinson

Research output: Contribution to journalArticle

18 Citations (Scopus)
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Abstract

A detailed mechanistic understanding of the malonoyl peroxide mediated dihydroxylation of alkenes is presented. The reaction is first order in both alkene and peroxide with stoichiometric water playing a dual role. An ionic mechanism is proposed and supported by the use of 18O isotopically labelled peroxide, a radical clock probe and DFT calculations. Hammett analysis suggests the reaction proceeds via a discrete carbocation intermediate which is consistent with the stereochemical outcome of the transformation. A subsequent Woodward-type 1,3-dioxolan-2-yl cation has been trapped in situ and the mechanism of hydrolysis defined by isotopic labelling studies. Stable reaction intermediates have been isolated and characterised by X-ray crystallographic analysis and minor competing reaction pathways identified.
Original languageEnglish
Pages (from-to)1777-1785
Number of pages9
JournalChemical Science
Volume5
Issue number5
Early online date19 Feb 2014
DOIs
Publication statusPublished - 1 May 2014

Keywords

  • stoichiometric water
  • hydrolysis
  • discrete carbocation

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