Mechanistic insights into the malonoyl peroxide syn-dihydroxylation of alkenes

Michael Rawling, Julian Rowley, Matthew Campbell, Alan Kennedy, John Parkinson, Nick Tomkinson

Research output: Contribution to journalArticle

17 Citations (Scopus)

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.
LanguageEnglish
Pages1777-1785
Number of pages9
JournalChemical Science
Volume2014
Issue number5
DOIs
Publication statusPublished - 2014

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Peroxides
Alkenes
Reaction intermediates
Discrete Fourier transforms
Labeling
Cations
Clocks
Hydrolysis
X rays
Water

Keywords

  • stoichiometric water
  • hydrolysis
  • discrete carbocation

Cite this

Rawling, Michael ; Rowley, Julian ; Campbell, Matthew ; Kennedy, Alan ; Parkinson, John ; Tomkinson, Nick. / Mechanistic insights into the malonoyl peroxide syn-dihydroxylation of alkenes. In: Chemical Science. 2014 ; Vol. 2014, No. 5. pp. 1777-1785.
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Mechanistic insights into the malonoyl peroxide syn-dihydroxylation of alkenes. / Rawling, Michael; Rowley, Julian; Campbell, Matthew; Kennedy, Alan; Parkinson, John; Tomkinson, Nick.

In: Chemical Science, Vol. 2014, No. 5, 2014, p. 1777-1785.

Research output: Contribution to journalArticle

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AU - Rowley, Julian

AU - Campbell, Matthew

AU - Kennedy, Alan

AU - Parkinson, John

AU - Tomkinson, Nick

PY - 2014

Y1 - 2014

N2 - 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.

AB - 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.

KW - stoichiometric water

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KW - discrete carbocation

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