Chemistry - A European Journal
10.1002/chem.201604504
COMMUNICATION
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In summary, we have developed the first nickel-catalyzed
decarbonylative borylation reaction of carboxylic acid esters.
This protocol provides a new possibility to cleave a stable ester
group while forming a versatile boron group. The broad
substrate scope, high reactivity and scalability of the method
suggest that this protocol can be a powerful alternative to the
existing methodologies for preparing organoboron compounds
from readily available precursors. It is important to note that the
newly developed protocol shows high chemoselectivity and that
functional groups such as C-OMe, C-For C-NCOR previously
used in Nickel catalyzed functional group interconversions
remain intact. Thus, the developed protocol will be of interest as
it allows to replace ester groups which can be used prior the
replacement as directing group in Friedel-Crafts reactions or
metal catalyzed CH-functionalizations. The method may also be
considered in retrosynthesis planning using the ester group as
directing group and at the same time placeholder for the boron
functionality which if required can easily functionalized to other
valuable products. Further mechanistic studies and other related
transformations are currently underway in our laboratories.
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L. Guo was supported by the China Scholarship Council.
Keywords: Decarbonylative cross-coupling • decarboxylation •
ester • C-O bond activation • CH borylation
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