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