Journal of the American Chemical Society
Article
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synergistic fashion, hence uncovering new reactivity profiles
counterintuitive at first sight. The attractiveness of this study is
based on the ability to couple readily available aryl or benzyl
esters with CO2 via the activation of traditionally considered
inert C(sp2)− and C(sp3)−O bonds. In this manner, this
technique can be visualized as a novel innovative bond
disconnection synthetic strategy while providing a previously
unrecognized opportunity for assembling valuable carboxylic
acids. The operational simplicity, the absence of air- or
moisture-sensitive reagents, together with the excellent
preparative scope and chemoselectivity profile of this method
holds great promise for the utilization of ester derivatives as a
powerful alternative to the commonly used organic halides in
catalytic carboxylation processes. Indeed, a number of relevant
phenyl acetic acids bearing heterocyclic motifs (Tables 5 and
7), which were inaccessible by our previous Ni-catalyzed
carboxylation of benzyl halides,9b are now within reach via C−
O bond-cleavage using benzyl ester derivatives. We believe
these results illustrate not only the unique outcome of C−O
electrophiles as substrates but also significantly increase the
flexibility in carboxylative protocols.
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While many C−O bond-cleavage reactions remain limited to
π-extended systems, this study demonstrates that a traceless
hemilabile directing group overcomes such limitation when
using C(sp3)−O motifs, a yet unexplored avenue in catalytic
reductive events using C−O electrophiles as counterparts.
Although additional investigations are warranted to expand the
scope and improve even further catalytic performance, we
anticipate that the excellent selectivity profile of this new
carboxylative protocol might serve as a reference source for
practitioners in the field. Further studies regarding the
extension to other coupling partners are currently underway
in our laboratories.
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ASSOCIATED CONTENT
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S
* Supporting Information
Experimental procedures, spectral data and crystallographic
data (CIF). This material is available free of charge via the
For related electrochemical carboxylative processes of organic halides,
see for example: (c) Amatore, C.; Jutand, A.; Khalil, F.; Nielsen, M. F.
J. Am. Chem. Soc. 1992, 114, 7076. (d) Ohkoshi, M.; Michinishi, J.−Y.;
Hara, S.; Senboku, H. Tetrahedron 2010, 66, 7732.
(10) (a) Fujihara, T.; Nogi, K.; Xu, T.; Terao, J.; Tsuji, Y. J. Am.
Chem. Soc. 2012, 134, 9106. (b) Tran-Vu, H.; Daugulis, O. ACS Catal.
2013, 3, 2417.
AUTHOR INFORMATION
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Corresponding Author
Funding
The authors declare no competing financial interests
(11) For recent reviews: (a) Mesganaw, T.; Garg, N. K. Org. Process
Res. Dev. 2013, 17, 29. (b) Yamaguchi, J.; Muto, K.; Itami, K. Eur. J.
Org. Chem. 2013, 19. (c) Correa, A.; Cornella, J.; Martin, R. Angew.
Chem., Int. Ed. 2013, 52, 1878. (d) Rosen, B. M.; Quasdorf, K. W.;
Wilson, D. A.; Zhang, N.; Resmerita, A.−M.; Garg, N. K.; Percec, V.
Chem. Rev. 2011, 111, 1346. (e) Li, B.-J.; Yu, D.-G.; Sun, C.-L.; Shi, Z.-
J. Chem.Eur. J. 2011, 17, 1728. (f) Yu, D.-G.; Li, B.-J.; Shi, Z.-J. Acc.
Chem. Res. 2010, 43, 1486.
(12) For selected references using aryl esters, see: (a) Guan, B.-T.;
Wang, Y.; Li, B.-J.; Yu, D.-G.; Shi, Z.-J. J. Am. Chem. Soc. 2008, 130,
14468. (b) Quasford, K. W.; Tian, X.; Garg, N. K. J. Am. Chem. Soc.
2008, 130, 14422. (c) Leowanawat, P.; Zhang, N.; Percec, V. J. Org.
Chem. 2012, 77, 1018. (d) Ehle, A. R.; Zhou, Q.; Watson, M. P. Org.
Lett. 2012, 14, 1202. (e) Li, B.-J.; Li, Y.-Z.; Lu, X.-Y.; Liu, J.; Guan, B.-
T.; Shi, Z.-J. Angew. Chem., Int. Ed. 2008, 47, 10124. (f) Shimasaki, T.;
Tobisu, M.; Chatani, N. Angew. Chem., Int. Ed. 2010, 49, 2929.
(g) Tobisu, M.; Yamakawa, K.; Shimasaki, T.; Chatani, N. Chem.
Commun. 2011, 47, 2946. (h) Muto, K.; Yamaguchi, J.; Itami, K. J. Am.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank ICIQ Foundation, the European Research Council
(ERC-277883) and MICINN (CTQ2012-34054) for financial
support. Johnson Matthey, Umicore and Nippon Chemical
Industrial are acknowledged for a gift of metal and ligand
sources. R.M. and A.C. thank MICINN for a RyC and JdC
fellowship. We thank Eddy Martin and Eduardo Escudero for
X-Ray crystallographic data.
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