Development of Molecular Complexity through Nitrene-Transfer Reactions Catalyzed by Copper and Silver Scorpionate Complexes

Manuel R. Rodríguez; M. Mar Díaz-Requejo; Pedro J. Pérez

doi:10.1055/s-0040-1706534

Synlett, Table of Contents

Synlett 2021; 32(08): 763-774
DOI: 10.1055/s-0040-1706534

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Development of Molecular Complexity through Nitrene-Transfer Reactions Catalyzed by Copper and Silver Scorpionate Complexes

Authors

Manuel R. Rodríguez
M. Mar Díaz-Requejo ∗

Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, 21007 Huelva, Spain Email: perez@dqcm.uhu.es Email: mmdiaz@dqcm.uhu.es
Pedro J. Pérez ∗

Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, 21007 Huelva, Spain Email: perez@dqcm.uhu.es Email: mmdiaz@dqcm.uhu.es

Abstract

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Abstract

For years, metal–nitrene-transfer reactions have been mainly directed toward C=C bond aziridination or C–H bond amidation reactions. In the last decade, multiple efforts have been made to develop new synthetic approaches to expand the applicability of this powerful tool, resulting in the synthesis of complex structures from relatively simple starting materials. Here, we present our contributions to the area with several novel and, to some degree, unexpected transformations developed by our research group. The catalysts for these nitrene-transfer reactions are copper or silver complexes bearing hydrotrispyrazolyl (scorpionate) ligands. These transformations have contributed to an expansion of the scope of organic compounds accessible by nitrene-transfer reactions and to an understanding of the reactivity of metallonitrene species toward the oxidation of less-explored organic substrates.

1 Introduction

2 Synthesis of 1,2-Dihydropyridines from Furans

3 Regio- and Stereoselective Aziridination of Dienes

4 Chemoselective Synthesis of Aminimides from Amines

5 Synthesis of Sulfinamides and Isothiazoles from Alkynes

6 Formation of Azetidines and Methylene Aziridines from Allenes

7 Conclusion

Key words - nitrene transfer - C–N bond formation - copper catalysis - silver catalysis - dihydropyridines - aminimides

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