Alkene oxyamination using malonoyl peroxides: preparation of pyrrolidines and isoxazolidines

Carla Alamillo-Ferrer, Jonathan M Curle, Stuart C Davidson, Simon C C Lucas, Stephen J Atkinson, Matthew Campbell, Alan R Kennedy, Nicholas C O Tomkinson

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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.
Original languageEnglish
Pages (from-to)6728-6740
Number of pages13
JournalJournal of Organic Chemistry
Volume83
Issue number12
Early online date29 May 2018
DOIs
Publication statusPublished - 15 Jun 2018

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Keywords

  • alkenes
  • organic synthesis
  • dihydroxylation

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