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 10.1021/acs.joc.8b00392.s001 https://acs.figshare.com/articles/journal_contribution/Alkene_Oxyamination_Using_Malonoyl_Peroxides_Preparation_of_Pyrrolidines_and_Isoxazolidines/6387371 Treatment of homoallylic <i>N</i>-tosyl amines or allylic <i>N</i>-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 <i>trans</i>-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. 2018-05-29 19:18:47 homoallylic N Mechanistic investigations show Pyrrolidine 1.5 equiv malonoyl peroxide stereoselective method selectivity access functionalized pyrrolidines sequence sulfonamide nucleophiles reactivity allylic N tosyl hydroxylamines dioxygenation oxidation nitrogen substituents alkene oxyamination proceeds isoxazolidine Preparation hydroxyl nucleophiles stereochemistry tosyl amines Isoxazolidines Treatment tran preference Malonoyl Peroxides Alkene Oxyamination inverting