An Organocopper(III) Fluoride Triggering C-CF 3 Bond Formation

Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross-coupling. The synthesis of [PPh ][Cu (CF ) F] (2), the first stable (isolable) Cu -F, was accomplished via chloride addition to [Cu (CF ) (py)] (1) yielding [PPh ][Cu (CF ) Cl(py)] (1⋅Cl), followed by treatment wi...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2024-03, Vol.63 (11), p.e202319412
Main Authors: Joven-Sancho, Daniel, Echeverri, Andrea, Saffon-Merceron, Nathalie, Contreras-García, Julia, Nebra, Noel
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross-coupling. The synthesis of [PPh ][Cu (CF ) F] (2), the first stable (isolable) Cu -F, was accomplished via chloride addition to [Cu (CF ) (py)] (1) yielding [PPh ][Cu (CF ) Cl(py)] (1⋅Cl), followed by treatment with AgF. The Cu halides 1⋅Cl and 2 were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X-ray diffraction (Sc-XRD) and elemental analysis (EA). Complex 2 proved capable of forging C-CF bonds from silyl-capped alkynes. In-depth mechanistic studies combining probes, theoretical calculations, trapping of intermediate 4 ([PPh ][Cu (CF ) (C≡CPh)]) and radical tests unveil the key role of the Cu acetylides that undergo facile 2e reductive elimination furnishing the trifluoromethylated alkynes (RC≡CCF ), which are industrially relevant synthons in drug discovery, pharma and agrochemistry.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202319412