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Alkene Oxyamination Using Malonoyl Peroxides: Preparation of Pyrrolidines and Isoxazolidines
journal contribution
posted on 2018-05-29, 19:18 authored by Carla Alamillo-Ferrer, Jonathan M. Curle, Stuart C. Davidson, Simon C. C. Lucas, Stephen J. Atkinson, Matthew Campbell, Alan R. Kennedy, Nicholas C. O. TomkinsonTreatment 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.
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homoallylic NMechanistic investigations showPyrrolidine1.5 equivmalonoyl peroxidestereoselective methodselectivityaccess functionalized pyrrolidinessequencesulfonamide nucleophilesreactivityallylic Ntosyl hydroxylaminesdioxygenationoxidationnitrogen substituentsalkene oxyamination proceedsisoxazolidinePreparationhydroxyl nucleophilesstereochemistrytosyl aminesIsoxazolidines TreatmenttranpreferenceMalonoyl PeroxidesAlkene Oxyaminationinverting
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