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Catalytic asymmetric synthesis of tertiary alkyl fluorides: Negishi cross-couplings of racemic ?,?-dihaloketones.

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 ?-halo-?-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 ?-fluoroketones, can be converted into an array of interesting organofluorine compounds.

SUBMITTER: Liang Y

PROVIDER: S-EPMC4004247 | biostudies-other | 2014 Apr

REPOSITORIES: biostudies-other

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Catalytic asymmetric synthesis of tertiary alkyl fluorides: Negishi cross-couplings of racemic α,α-dihaloketones.

Liang Yufan Y Fu Gregory C GC

Journal of the American Chemical Society 20140331 14

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 (o ...[more]

PMID: 24678878

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