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of carbon monoxide provides palladium acyl complex A.
Exchange of the bromide counterion for a carbonate with
simultaneous formation of CsBr affords intermediate B. This
complex can then either participate in C−H bond activation of the
polyfluoroarene, through transitionstate C or undergo reductive
60
65
70
75
80
2011, 13, 3174-3177.
DOI: 10.1039/C4CC09303H
6
For selected recent reviews and highlights on C-H activation, see: (a)
N. Kuhl, M. N. Hopkinson, J. Wencel-Delord and F. Glorius, Angew.
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5
elimination
forming
acylcarbonate
E.
Subsequent
decarboxylation of E, would form the carboxylic acid observed as
the major side-product, thus explaining its formation even under
strictly anhydrous conditions. On the other hand, if C−H
10 activation resulting in intermediate D is faster than reductive
elimination from B, then D only needs to undergo reductive
elimination to form the desired product and regenerate the
palladium(0) catalyst. Alternatively, trifluoroacetate may affect
the deprotonative palladation with subsequent deprotonation by
15 the base, thus acting as a proton shuttle.23
7
8
Conclusions
In summary, the first intermolecular Pd-catalyzed carbonylative
coupling of aryl bromides relying on C−H activation has been
presented. The transformation proceeds under relatively mild
20 conditions and does not require an additional transition metal to
furnish an organometallic species for transmetallation.24 The
methodology successfully transforms a variety of aryl- and
9
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Am. Chem. Soc. 2010, 132, 17378-17380.
heteroaryl
bromides
into
their
corresponding
benzopolyfluorophenones. Similarly, it was shown that a number
25 of other polyfluoroarenes are also competent substrates for this
transformation. Isotopic labeling was demonstrate to be efficient,
by simply applying [13C]-COgen, while the synthetic usefulness
of this reaction was underlined by the synthesis of a NOS
inhibitor. Lastly, a mechanistic scenario, which also accounts for
30 the experimentally observed byproduct, was proposed.
12 (a) K. Inamoto, J. Kadokawa and Y. Kondo, Org. Lett. 2013, 15,
90
3962-3965; (b) Z. H. Guan, M. Chen and Z. H. Ren, J. Am. Chem.
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16 (a) M. Kranenburg, Y. E. M. van der Burgt, P. C. J. Kamer, P. W. N.
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18 E. Vitaku, D. T. Smith and J. T. Njardarson, J. Med. Chem. 2014,
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95
Acknowledgements
100
105
110
115
120
125
130
We deeply appreciative of generous financial support from the
Danish National Research Foundation, (grant no. DNRF59), the
Villum Foundation, the Danish Council for Independent
35 Research: Technology and Production Sciences, the Lundbeck
Foundation, the Carlsberg Foundation, and Aarhus University.
Furthermore, we thank the Chinese Scholarship Council for a
grant to Z. L.
Notes and references
40
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22 See Supporting Information for details.
5
For selected transformation installing polyfluoroarenes, see: (a) M.
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