Catalytic Nitrene Transfer To Alkynes: A Novel and Versatile Route for the Synthesis of Sulfinamides and Isothiazoles

A novel transformation is reported for the reaction of terminal or internal alkynes with the nitrene precursor PhI=NTs (Ts=p‐toluenesulfonyl) in the presence of catalytic amounts of TpBr3Cu(NCMe) (TpBr3=hydrotris(3,4,5‐tribromo‐pyrazolylborate). Two products containing an imine functionality have be...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2017-10, Vol.56 (42), p.12842-12847
Main Authors: Rodríguez, Manuel R., Beltrán, Álvaro, Mudarra, Ángel L., Álvarez, Eleuterio, Maseras, Feliu, Díaz‐Requejo, M. Mar, Pérez, Pedro J.
Format: Article
Language:English
Subjects:
alkyne functionalization
Alkynes
Catalysis
copper catalysis
isothiazoles
nitrene transfer
sulfinamides
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Summary:A novel transformation is reported for the reaction of terminal or internal alkynes with the nitrene precursor PhI=NTs (Ts=p‐toluenesulfonyl) in the presence of catalytic amounts of TpBr3Cu(NCMe) (TpBr3=hydrotris(3,4,5‐tribromo‐pyrazolylborate). Two products containing an imine functionality have been isolated from the reaction mixtures, identified as sulfinamides and isothiazoles. The former correspond to the formal reduction of the sulfone group into sulfoxide, whereas the latter involves the insertion of an alkyne carbon atom into the aromatic ring of the N‐tosyl moiety. Metal‐catalyzed ring formation: The copper‐catalyzed reaction of alkynes and the nitrene precursor PhI=N‐Ts (Ts=p‐toluenesulfonyl) affords sulfinamides and isothiazoles in a metal‐mediated nitrene transfer reaction. The mechanism of this novel transformation has been proposed from experimental data as well as DFT calculations.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201705664