Organic Letters
Letter
of the reaction conditions, we were pleased to find that arylated
pyridines 4 could be obtained in good yields via a C−H
arylation/copper(I) mediated decarboxylation sequence
Y.; Li, J.; Yang, S.; Yan, H.; Huang, G. Org. Lett. 2013, 15, 5194. (h) Deb,
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(
Scheme 5). The decarboxylation proceeded equally well at C3
4aa−4ea), C2 (4ja), and C4 (4na). To the best of our
(
3
57, 1143. (k) Kan, J.; Huang, S.; Lin, J.; Zhang, M.; Su, W. Angew.
knowledge, this represents the first strategy for the one-pot
formation of directing-group-free, C4-arylated pyridines as single
regioisomers.
Chem., Int. Ed. 2015, 54, 2199.
̈
̈ ̈
rbuz, N.; Ozdemir, I.; Çetinkaya, B. Tetrahedron Lett. 2005,
(
4) (a) Gu
4
6, 2273. (b) Lafrance, M.; Rowley, C. N.; Woo, T. K.; Fagnou, K. J. Am.
In conclusion, we have demonstrated that the directing power
of carboxylic acids could be successfully harnessed to
regioselectively C−H arylate pyridines at the C3 and C4
positions. Starting from simple pyridinecarboxylic acids and
inexpensive chloro- and bromoarenes, a variety of pyridine
biaryls could be accessed with high regioselectivity and good
yields. Furthermore, the carboxylic acids can be used as traceless
directing groups via an efficient one-pot C−H arylation/
copper(I)-mediated decarboxylation sequence allowing the
formation of directing group free pyridine biaryls.
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6
(k) Shang, Y.; Jie, X.; Zhao, H.; Hu, P.; Su, W. Org. Lett. 2014, 16, 416.
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ASSOCIATED CONTENT
Supporting Information
■
1
37, 15636. (n) He, Y.; Wu, Z.; Ma, C.; Zhou, X.; Liu, X.; Wang, X.;
*
S
Huang, G. Adv. Synth. Catal. 2016, 358, 375. (o) Senaweera, S.; Weaver,
J. D. J. Am. Chem. Soc. 2016, 138, 2520. (p) Yamada, S.; Murakami, K.;
Itami, K. Org. Lett. 2016, 18, 2415. (q) Jiao, J.; Murakami, K.; Itami, K.
Chem. Lett. 2016, 45, 529.
previously unknown compounds (PDF)
(5) (a) Graber, S.; Doyle, K.; Neuburger, M.; Housecroft, C. E.;
Constable, E. C.; Costa, R. D.; Ortí, E.; Repetto, D.; Bolink, H. J. J. Am.
Chem. Soc. 2008, 130, 14944. (b) Wong, W.-Y.; Ho, C.-L. Coord. Chem.
Rev. 2009, 253, 1709. (c) Robson, K. C.; Koivisto, B. D.; Berlinguette, C.
P. Inorg. Chem. 2012, 51, 1501.
AUTHOR INFORMATION
■
*
*
(6) (a) Vetrichelvan, M.; Valiyaveettil, S. Chem. - Eur. J. 2005, 11, 5889.
(b) Oyston, S.; Wang, C.; Perepichka, I. F.; Batsanov, A. S.; Bryce, M. R.;
Ahn, J. H.; Petty, M. C. J. Mater. Chem. 2005, 15, 5164.
ORCID
(7) (a) Michael, J. P. Nat. Prod. Rep. 2005, 22, 627. (b) Kassis, P.;
Brzeszcz, J.; Ben
Guillouzo, C.; Lewin
Merour, J.-Y. Eur. J. Med. Chem. 2011, 46, 5416. (c) O’Neill, P. M.;
́
et
́
eau, V.; Lozach, O.; Meijer, L.; Le Guev
́
́
el, R.;
Notes
́
Ward, S. A. Angew. Chem., Int. Ed. 2015, 54, 13504. (d) Xie, Y.; Chi, H.-
W.; Guan, A.-Y.; Liu, C.-L.; Ma, H.-J.; Cui, D.-L. J. Agric. Food Chem.
The authors declare no competing financial interest.
2
014, 62, 12491. (e) Xie, Y.; Chi, H.-W.; Guan, A.-Y.; Liu, C.-L.; Ma, H.-
ACKNOWLEDGMENTS
We gratefully acknowledge the Engineering and Physical
Sciences Research Council and Syngenta for a CASE studentship
to A.J.), and the EPSRC National Mass Spectrometry Service
Swansea).
■
J.; Cui, D.-L. Bioorg. Med. Chem. 2016, 24, 428. (f) Epp, J. B.; et al. Bioorg.
Med. Chem. 2016, 24, 362.
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2007, 129, 9879. (b) Miura, M.; Satoh, T. Synthesis 2010, 2010, 3395.
(
(
(c) Engle, K. M.; Mei, T.-S.; Wasa, M.; Yu, J.-Q. Acc. Chem. Res. 2012, 45,
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88. (d) Wu, Z.; Chen, S.; Hu, C.; Li, Z.; Xiang, H.; Zhou, X.
ChemCatChem 2013, 5, 2839. (e) Liu, Y.-J.; Xu, H.; Kong, W.-J.; Shang,
M.; Dai, H.-X.; Yu, J.-Q. Nature 2014, 515, 389. (f) Zhu, C.; Zhang, Y.;
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