Chemistry - A European Journal
10.1002/chem.201904842
COMMUNICATION
In summary, we have developed a new protocol for the nickel-
catalyzed ipso-borylation and ipso-silylation of aldehydes. This new
method relies on the use of readily available aldehydes in
combination with low amounts of a nickel catalyst and provides the
borylated and silylated products in one step under base-free
conditions. Previously reported protocols for the synthesis of
organoborons and organosilicons often use pre-formed or more
sensitive organometallic reagents which may not always be
compatible with functional groups. Thus, the reported base-free
protocol constitutes a valuable complementary approach which can
also be applied for the interconversion of more complex aldehydes in
which the carbonyl group has been used as a directing group for C-
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H functionalizations prior to the ipso-substitution. Importantly, this
protocol shows good functional group tolerance and broad substrate
scope including natural product derivatives, which unlocks the
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sophisticated molecules. Regarding the mechanism of this so far
unprecedented ipso-functionalization of aldehydes we postulate that
the reaction proceeds through C(acyl)-H bond activation with
subsequent hydride transfer as a key step. Given the simplicity and
practicability of the strategy, it is anticipated that it should find further
applications in synthesis, retrosynthesis, and late-stage
functionalization.
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This research was supported by King Abdullah University of
Science and Technology (KAUST) Office of Sponsored
Research under award number URF/1/3030-01
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Keywords: Borylation • Silylation • Aldehyde • Decarbonylative
cross-coupling • Nickel catalysis
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