Nickel-Catalyzed Alkyl–Alkyl Cross-Couplings of Fluorinated Secondary Electrophiles: A General Approach to the Synthesis of Compounds having a Perfluoroalkyl Substituent
- Creators
-
Liang, Yufan
-
Fu, Gregory C.
Abstract
Fluorinated organic molecules are of interest in fields ranging from medicinal chemistry to polymer science. Described herein is a mild, convenient, and versatile method for the synthesis of compounds bearing a perfluoroalkyl group attached to a tertiary carbon atom by using an alkyl–alkyl cross-coupling. A nickel catalyst derived from NiCl_2⋅glyme and a pybox ligand achieves the coupling of a wide range of fluorinated alkyl halides with alkylzinc reagents at room temperature. A broad array of functional groups is compatible with the reaction conditions, and highly selective couplings can be achieved on the basis of differing levels of fluorination. A mechanistic investigation has established that the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) inhibits cross-coupling under these conditions and that a TEMPO–electrophile adduct can be isolated.
Additional Information
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: April 11, 2015; Revised: May 3, 2015; Article first published online: 12 June 2015. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871) and the Gordon and Betty Moore Foundation (Caltech Center for Catalysis and Chemical Synthesis). We thank Dr. Nathan D. Schley for helpful discussions.Attached Files
Accepted Version - nihms711211.pdf
Supplemental Material - anie_201503297_sm_miscellaneous_information.pdf
Files
Name | Size | Download all |
---|---|---|
md5:cab3aed2421b3977d53bea437429c910
|
1.4 MB | Preview Download |
md5:d4e916281dc0d78057bfa66d2857e69b
|
659.6 kB | Preview Download |
Additional details
- PMCID
- PMC4521909
- Eprint ID
- 58302
- Resolver ID
- CaltechAUTHORS:20150617-075445770
- NIH
- R01-GM62871
- Gordon and Betty Moore Foundation
- Created
-
2015-06-17Created from EPrint's datestamp field
- Updated
-
2022-06-01Created from EPrint's last_modified field