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Copper‐Catalyzed N−F Bond Activation for Uniform Intramolecular C−H Amination Yielding Pyrrolidines and Piperidines
Author(s) -
Bafaluy Daniel,
MuñozMolina José María,
FunesArdoiz Ignacio,
Herold Sebastian,
de Aguirre Adiran J.,
Zhang Hongwei,
Maseras Feliu,
Belderrain Tomás R.,
Pérez Pedro J.,
Muñiz Kilian
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201902716
Subject(s) - intramolecular force , pyrrolidine , amination , catalysis , chemoselectivity , chemistry , piperidine , catalytic cycle , copper , combinatorial chemistry , methylamines , medicinal chemistry , stereochemistry , organic chemistry
The dual function of the N−F bond as an effective oxidant and subsequent nitrogen source in intramolecular aliphatic C−H functionalization reactions is explored. Copper catalysis is demonstrated to exercise full regio‐ and chemoselectivity control, which opens new synthetic avenues to nitrogenated heterocycles with predictable ring sizes. For the first time, a uniform catalysis manifold has been identified for the construction of both pyrrolidine and piperidine cores. The individual steps of this new copper oxidation catalysis were elucidated by control experiments and computational studies, clarifying the singularity of the N−F function and characterizing the catalytic cycle to be based on a copper(I/II) manifold.