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

Manuel R Rodríguez; Álvaro Beltrán; Ángel L Mudarra; Eleuterio Álvarez; Feliu Maseras; M Mar Díaz-Requejo; Pedro J Pérez

doi:10.1002/anie.201705664

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

Angew Chem Int Ed Engl. 2017 Oct 9;56(42):12842-12847. doi: 10.1002/anie.201705664. Epub 2017 Aug 1.

Authors

Manuel R Rodríguez¹, Álvaro Beltrán¹, Ángel L Mudarra², Eleuterio Álvarez³, Feliu Maseras^{2

4}, M Mar Díaz-Requejo¹, Pedro J Pérez¹

Affiliations

¹ Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en, Química Sostenible, Departamento de Química, Universidad de Huelva, Campus de El Carmen s/n, 21007, Huelva, Spain.
² Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans, 16, 43007, Tarragona, Spain.
³ Instituto de Investigaciones Químicas, CSIC-Universidad de Sevilla, Spain.
⁴ Departament de Química, Universitat Autònoma de Barcelona, 08193, Bellaterra, Spain.

PMID: 28707748
DOI: 10.1002/anie.201705664

Abstract

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 Tp^Br3 Cu(NCMe) (Tp^Br3 =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.

Keywords: alkyne functionalization; copper catalysis; isothiazoles; nitrene transfer; sulfinamides.

Publication types

Research Support, Non-U.S. Gov't