Journal of the American Chemical Society
Communication
proceed in other carbonylation reactions,24 also undergo clean
coupling (6q). The formation of acid chlorides also allows the
use of other, even less nucleophilic substrates in carbonylation.
Nitrogen-containing heterocycles are known to react with acid
chlorides but are rarely applied in palladium-catalyzed carbon-
ylations, likely due to their poor nucleophilicity and coordinating
ability.25 As shown in 6r−6s, these substrates can all be effectively
aroylated in high yields. The mild heating required for the latter is
not due to catalysis but to the sluggish reaction of these
heterocycles with acid chlorides (eqs S3, S4). As far as we are
aware, this represents a novel platform to perform amino-
carbonylations under ambient conditions with a broad range of
reagents.
In conclusion, these results demonstrate a new approach to
construct acid chlorides via the palladium-catalyzed carbon-
ylation of aryl halides. This transformation is mediated by
combination of the bulky, electron-rich PtBu3, chloride, and
carbon monoxide coordination, which together allows the rapid
reductive elimination of acid chloride under mild conditions.
Considering the availability of aryl halides and the diverse utility
of acid chlorides, this approach should prove equally applicable
to the efficient generation of a range of acid chlorides or acid
chloride-derived products. Studies directed toward the latter are
currently underway.
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ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental procedures, characterization and crystallographic
data. This material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
■
(16) (a) Neumann, H.; Brennfuhrer, A.; Groß, P.; Riermeier, T.;
̈
Almena, J.; Beller, M. Adv. Synth. Catal. 2006, 348, 1255. (b) Berger, P.;
Bessmernykh, A.; Caille, J.-C.; Mignonac, S. Synthesis 2006, 3106.
(c) Martinelli, J. R.; Watson, D. A.; Freckmann, D. M. M.; Barder, T. E.;
Buchwald, S. L. J. Org. Chem. 2008, 73, 7102.
Notes
The authors declare no competing financial interest.
(17) (a) Jeffery, T. J. Chem. Soc., Chem. Commun. 1984, 1287.
(b) Jeffery, T. Tetrahedron Lett. 1985, 26, 2667. (c) Reetz, M. T.;
Westermann, E. Angew. Chem., Int. Ed. 2000, 39, 165. (d) Carrow, B. P.;
Hartwig, J. F. J. Am. Chem. Soc. 2010, 132, 79.
(18) Korsager, S.; Taaning, R. H.; Skrydstrup, T. J. Am. Chem. Soc.
2013, 135, 2891.
ACKNOWLEDGMENTS
■
We thank Laure Kayser, Zhijie Chua, and Prof. Scott Bohle for
their assistance in crystallography. We thank NSERC, the
Canadian Foundation for Innovation (CFI), and the FQRNT
supported Centre for Green Chemistry and Catalysis for funding
this research.
(19) (a) Stambuli, J. P.; Incarvito, C. D.; Buhl, M.; Hartwig, J. F. J. Am.
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Chem. Soc. 2004, 126, 1184. (b) Sergeev, A. G.; Spannenberg, A.; Beller,
M. J. Am. Chem. Soc. 2008, 130, 15549.
(20) Reductive elimination may also occur via an ionic (PtBu3)
(CO)nPd(COPh)+ Cl−. Catalytic acid chloride formation proceeds at
similar rates in polar (acetonitrile) and nonpolar (toluene) solvents,
consistent with a neutral intermediate. Nevertheless, an ionic pathway
cannot be ruled out.
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