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ChemComm
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β-iodohydrin, which is in situ produced from the epoxide and NaI,
reacts with (dppf)palladium(0) species to give β-hydroxyalkyl
radical (I) and an LnPdI complex. Addition of the hydroxyalkyl
radical (I) at the α-position of the C-C double bond in cinnamic acid
would give the benzylic radical II. Next, the radical II combines with
(Ln)PdI to form alkylpalladium(II) species III. Finally,
decarboxylation of the Pd(II) species to generate the product while
regenerating the Pd(0) species.
DOI: 10.1039/C9CC04795F
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Scheme 7 Proposed reaction mechanism.
In summary, we have developed the first Pd-catalyzed
decarboxylative cross-coupling of α,β-unsaturated carboxylic acid
with epoxides. The product was obtained as a mixture of
diastereomers favoring the anti diastereomer of the cyclic
epoxides. Reactions with β-monosubstituted and β-disubstituted
unsaturated carboxylic acids proceed with moderate to good
yields and conjugated diene unsaturated carboxylic acids showed
moderate reactivity. This methodology also provides access to
diverse array of substituted homoallylic alcohols, which are
valuable structural fragments in organic synthesis. It also provides
a route for the modification of complex organic molecules
containing α,β-unsaturated carboxylic acids.
Conflicts of interest
There are no conflicts to declare.
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4 | J. Name., 2012, 00, 1-3
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