Mechanistic insights into the malonoyl peroxide syn-dihydroxylation of alkenes

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Rawling, Michael J. and Rowley, Julian H. and Campbell, Matthew and Kennedy, Alan R. and Parkinson, John A. and Tomkinson, Nicholas C. O. (2014) Mechanistic insights into the malonoyl peroxide syn-dihydroxylation of alkenes. Chemical Science, 5 (5). pp. 1777-1785. ISSN 2041-6539 (https://doi.org/10.1039/c3sc53256a)

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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.

ORCID iDs

Rawling, Michael J., Rowley, Julian H., Campbell, Matthew, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Parkinson, John A. ORCID logoORCID: https://orcid.org/0000-0003-4270-6135 and Tomkinson, Nicholas C. O. ORCID logoORCID: https://orcid.org/0000-0002-5509-0133;
  • Item type:Article
    ID code:47420
    Dates:
    Date
    Event
    1 May 2014
    Published
    19 February 2014
    Published Online
    18 February 2014
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:09 Apr 2014 13:05
    Last modified:11 Nov 2024 10:39
    URI:https://strathprints.strath.ac.uk/id/eprint/47420
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