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Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones

Liang, Yufan and Fu, Gregory C. (2014) Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones. Journal of the American Chemical Society, 136 (14). pp. 5520-5524. ISSN 0002-7863. PMCID PMC4004247. http://resolver.caltech.edu/CaltechAUTHORS:20140408-083523386

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja501815pDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja501815pPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja501815pPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4004247/PubMed CentralArticle
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
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.
Funders:
Funding AgencyGrant Number
NIHR01-GM62871
NSFCHE-0639094
Gordon and Betty Moore FoundationUNSPECIFIED
PubMed Central ID:PMC4004247
Record Number:CaltechAUTHORS:20140408-083523386
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140408-083523386
Official Citation:Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones Yufan Liang and Gregory C. Fu Journal of the American Chemical Society 2014 136 (14), 5520-5524
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44725
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 Apr 2014 16:50
Last Modified:21 Jul 2017 17:17

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