Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination

[Image: see text] We have recently developed a method for the synthesis of pyrrolidines and piperidines via intramolecular C–H amination of N-fluoride amides using [Tp(x)CuL] complexes as precatalysts [Tp(x) = tris(pyrazolyl)borate ligand and L = THF or CH(3)CN]. Herein, we report mechanistic studie...

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Autores principales: Muñoz-Molina, José María, Bafaluy, Daniel, Funes-Ardoiz, Ignacio, de Aguirre, Adiran, Maseras, Feliu, Belderrain, Tomás R., Pérez, Pedro J., Muñiz, Kilian
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9092462/
https://www.ncbi.nlm.nih.gov/pubmed/35572769
http://dx.doi.org/10.1021/acs.organomet.2c00095
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author Muñoz-Molina, José María
Bafaluy, Daniel
Funes-Ardoiz, Ignacio
de Aguirre, Adiran
Maseras, Feliu
Belderrain, Tomás R.
Pérez, Pedro J.
Muñiz, Kilian
author_facet Muñoz-Molina, José María
Bafaluy, Daniel
Funes-Ardoiz, Ignacio
de Aguirre, Adiran
Maseras, Feliu
Belderrain, Tomás R.
Pérez, Pedro J.
Muñiz, Kilian
author_sort Muñoz-Molina, José María
collection PubMed
description [Image: see text] We have recently developed a method for the synthesis of pyrrolidines and piperidines via intramolecular C–H amination of N-fluoride amides using [Tp(x)CuL] complexes as precatalysts [Tp(x) = tris(pyrazolyl)borate ligand and L = THF or CH(3)CN]. Herein, we report mechanistic studies on this transformation, which includes the isolation and structural characterization of a fluorinated copper(II) complex, [(Tp(iPr2)OH)CuF] [Tp(iPr) = hydrotris(3,5-diisopropylpyrazolyl)borate], pertinent to the mechanistic pathway. The effects of the nature of the Tp(x) 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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spelling pubmed-90924622022-05-11 Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination Muñoz-Molina, José María Bafaluy, Daniel Funes-Ardoiz, Ignacio de Aguirre, Adiran Maseras, Feliu Belderrain, Tomás R. Pérez, Pedro J. Muñiz, Kilian Organometallics [Image: see text] We have recently developed a method for the synthesis of pyrrolidines and piperidines via intramolecular C–H amination of N-fluoride amides using [Tp(x)CuL] complexes as precatalysts [Tp(x) = tris(pyrazolyl)borate ligand and L = THF or CH(3)CN]. Herein, we report mechanistic studies on this transformation, which includes the isolation and structural characterization of a fluorinated copper(II) complex, [(Tp(iPr2)OH)CuF] [Tp(iPr) = hydrotris(3,5-diisopropylpyrazolyl)borate], pertinent to the mechanistic pathway. The effects of the nature of the Tp(x) 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. American Chemical Society 2022-04-29 2022-05-09 /pmc/articles/PMC9092462/ /pubmed/35572769 http://dx.doi.org/10.1021/acs.organomet.2c00095 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Muñoz-Molina, José María
Bafaluy, Daniel
Funes-Ardoiz, Ignacio
de Aguirre, Adiran
Maseras, Feliu
Belderrain, Tomás R.
Pérez, Pedro J.
Muñiz, Kilian
Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination
title Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination
title_full Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination
title_fullStr Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination
title_full_unstemmed Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination
title_short Mechanistic Studies on the Synthesis of Pyrrolidines and Piperidines via Copper-Catalyzed Intramolecular C–H Amination
title_sort mechanistic studies on the synthesis of pyrrolidines and piperidines via copper-catalyzed intramolecular c–h amination
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9092462/
https://www.ncbi.nlm.nih.gov/pubmed/35572769
http://dx.doi.org/10.1021/acs.organomet.2c00095
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