Rhodium‐Catalyzed Cyclization of O,ω‐Unsaturated Alkoxyamines: Formation of Oxygen‐Containing Heterocycles

O,ω‐Unsaturated N‐tosyl alkoxyamines undergo unexpected RhIII‐catalyzed intramolecular cyclization by oxyamination to produce oxygen‐containing heterocycles. Mechanistic studies show that an aziridine intermediate seems to be responsible for the formation of the heterocycles, possibly via a RhV spec...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-01, Vol.57 (2), p.574-578
Main Authors: Escudero, Julien, Bellosta, Véronique, Cossy, Janine
Format: Article
Language:English
Subjects:
alkenes
Catalysis
Chemical Sciences
cyclizations
Oxygen
oxygen-containing heterocycles
Physics
Rhodium
synthetic methods
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Summary:O,ω‐Unsaturated N‐tosyl alkoxyamines undergo unexpected RhIII‐catalyzed intramolecular cyclization by oxyamination to produce oxygen‐containing heterocycles. Mechanistic studies show that an aziridine intermediate seems to be responsible for the formation of the heterocycles, possibly via a RhV species. Unexpected reactivity: Functionalized tetrahydrofurans were unexpectedly obtained instead of the intended isoxazolidines. The reaction proceeds from N‐tosyl O,ω‐unsaturated alkoxyamines and a known rhodium(III)‐catalyzed allylic C−H activation protocol. The scope and limitations of this surprising reaction are described. A mechanism, involving a rhodium(V) nitrenoid and an aziridination step, is discussed.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201710895