Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones
- Creators
- Liang, Yufan
-
Fu, Gregory C.
Abstract
The development of new approaches to the construction of fluorine-containing target molecules is important for a variety of scientific disciplines, including medicinal chemistry. In this Article, we describe a method for the catalytic enantioselective synthesis of tertiary alkyl fluorides through Negishi reactions of racemic α-halo-α-fluoroketones, which represents the first catalytic asymmetric cross-coupling that employs geminal dihalides as electrophiles. Thus, selective reaction of a C–Br (or C–Cl) bond in the presence of a C–F bond can be achieved with the aid of a nickel/bis(oxazoline) catalyst. The products of the stereoconvergent cross-couplings, enantioenriched tertiary α-fluoroketones, can be converted into an array of interesting organofluorine compounds.
Additional Information
© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: February 20, 2014; Published: March 31, 2014. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871). We thank Trixia M. Buscagan, Dr. Nathan D. Schley, Dr. Michael K. Takase (X-ray Crystallography Facility; a Bruker KAPPA APEX II X-ray diffractometer was purchased via NSF CRIF:MU award CHE-0639094 to the California Institute of Technology), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for assistance. The authors declare no competing financial interest.Attached Files
Published - ja501815p.pdf
Supplemental Material - ja501815p_si_001.cif
Supplemental Material - ja501815p_si_002.cif
Supplemental Material - ja501815p_si_003.cif
Supplemental Material - ja501815p_si_004.cif
Supplemental Material - ja501815p_si_005.cif
Supplemental Material - ja501815p_si_006.pdf
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Additional details
- PMCID
- PMC4004247
- Eprint ID
- 44725
- Resolver ID
- CaltechAUTHORS:20140408-083523386
- NIH
- R01-GM62871
- NSF
- CHE-0639094
- Gordon and Betty Moore Foundation
- Created
-
2014-04-08Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field