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Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C-H
José María Muñoz-Molina1, Daniel Bafaluy2, Ignacio Funes-Ardoiz2
1Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, 21007 Huelva, Spain.
Abstract:
We have recently developed a method for the synthesis of pyrrolidines and piperidines via intramolecular C-H amination of N-fluoride amides using [Tp CuL] complexes as precatalysts [Tp = tris(pyrazolyl)borate ligand and L = THF or CH3CN]. Herein, we report mechanistic studies on this transformation, which includes the isolation and structural characterization of a fluorinated copper(II) complex, [(TpiPr2OH)CuF] [TpiPr = hydrotris(3,5-diisopropylpyrazolyl)borate], pertinent to the mechanistic pathway. The effects of the nature of the Tp ligand in the copper catalyst as well as of the halide in the N-X amides employed as reactants have been investigated both from experimental and computational perspectives.
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