Alkene oxyamination using malonoyl peroxides : preparation of pyrrolidines and isoxazolidines

Alamillo-Ferrer, Carla and Curle, Jonathan M and Davidson, Stuart C and Lucas, Simon C C and Atkinson, Stephen J and Campbell, Matthew and Kennedy, Alan R and Tomkinson, Nicholas C O (2018) Alkene oxyamination using malonoyl peroxides : preparation of pyrrolidines and isoxazolidines. Journal of Organic Chemistry, 83 (12). pp. 6728-6740. ISSN 0022-3263 (https://doi.org/10.1021/acs.joc.8b00392)

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Abstract

Treatment of homoallylic N-tosyl amines or allylic N-tosyl hydroxylamines with 1.5 equiv of a malonoyl peroxide provides a stereoselective method to access functionalized pyrrolidines and isoxazolidines. This metal free alkene oxyamination proceeds in 50-85% yield and up to 13:1 trans-selectivity. In addition, the relative stereochemistry of the oxygen and nitrogen substituents can be inverted through an oxidation/reduction sequence or inverting the stereochemistry of the starting alkene. Mechanistic investigations show a higher reactivity for hydroxyl nucleophiles over sulfonamide nucleophiles revealing a preference for dioxygenation over oxyamination.

ORCID iDs

Alamillo-Ferrer, Carla ORCID logoORCID: https://orcid.org/0000-0003-3607-846X, Curle, Jonathan M, Davidson, Stuart C ORCID logoORCID: https://orcid.org/0000-0003-2202-2625, Lucas, Simon C C ORCID logoORCID: https://orcid.org/0000-0003-0636-7164, Atkinson, Stephen J, Campbell, Matthew ORCID logoORCID: https://orcid.org/0000-0002-6003-7257, Kennedy, Alan R ORCID logoORCID: https://orcid.org/0000-0003-3652-6015 and Tomkinson, Nicholas C O ORCID logoORCID: https://orcid.org/0000-0002-5509-0133;
  • Item type:Article
    ID code:66514
    Dates:
    Date
    Event
    15 June 2018
    Published
    29 May 2018
    Published Online
    9 February 2018
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:10 Jan 2019 11:36
    Last modified:11 Nov 2024 12:11
    URI:https://strathprints.strath.ac.uk/id/eprint/66514
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