Organic Letters
Letter
(5) Martin, R.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129, 3844.
concept is shown to be applicable to other chemistry in the
literature, namely the direct use of organolithium reagents in
cross-coupling.Giventhattheultimatesourceofchemoselectivity
comes from the relative rate of transmetalation in comparison
with potential side reactions, further improvement of this method
is anticipated with more study into the parameters that influence
either of these rates.
(6) Manolikakes, G.; Knochel, P. Angew. Chem., Int. Ed. 2009, 48, 205.
(7)Attenuating the reactivityof Grignardreagents with, e.g., additives is
an alternative protocol for enhancing chemoselectivity. See: (a) Wang,
X.-j.; Zhang, L.; Sun, X.; Xu, Y.; Krishnamurthy, D.; Senanayake, C. H.
Org. Lett. 2005, 7, 5593. (b) Wang, X.-j.; Sun, X.; Zhang, L.; Xu, Y.;
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(8) The use of aryl chlorides as starting material is a challenging but an
important goal due to their low cost and molecular weight. (a) Grushin,
V. V.; Alper, H. Chem. Rev. 1994, 94, 1047. (b) Littke, A. F.; Fu, G. C.
Angew. Chem., Int. Ed. 2002, 41, 4176.
ASSOCIATED CONTENT
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S
* Supporting Information
(9)(a)Guerinot, A.;Reymond, S.;Cossy, J. Angew. Chem., Int. Ed. 2007,
46, 6521. (b) Daifuku, S. L.; Kneebone, J. L.; Snyder, B. E. R.; Neidig, M.
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(h) Steib, A. K.; Kuzmina, O. M.; Fernandez, S.; Flubacher, D.; Knochel,
P. J. Am. Chem. Soc. 2013, 135, 15346. (i) Iglesias, M. J.; Prieto, A.;
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(k) Liu, N.;Wang, Z.-X. J. Org. Chem. 2011, 76, 10031. (l) Frlan, R.; Sova,
TheSupportingInformationisavailablefreeofchargeontheACS
Experimental procedures, characterization of organic
molecules, optimization tables, robustness screen data,
scope limitations, electrospray mass spectrometry experi-
AUTHOR INFORMATION
Corresponding Author
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Notes
The authors declare no competing financial interest.
̌
M.; Gobec, S.; Stavber, G.; Casar, Z. J. Org. Chem. 2015, 80, 7803.
(m) Malhotra, S.; Seng, P. S.; Koenig, S. G.; Deese, A. J.; Ford, K. A. Org.
Lett. 2013, 15, 3698. (n) Gulak, S.; Stepanek, O.; Malberg, J.; Rad, B. R.;
Kotora, M.; Wolf, R.; Jacobi von Wangelin, A. Chem. Sci. 2013, 4, 776.
(o) Chua, Y.-Y.; Duong, H. A. Chem. Commun. 2014, 50, 8424. (p) Zeng,
J.; Liu, K. M.; Duan, X. F. Org. Lett. 2013, 15, 5342. (q) Vechorkin, O.;
Proust, V.; Hu, X. J. Am. Chem. Soc. 2009, 131, 9756. (r) Iglesias, M. J.;
Prieto, A.; Nicasio, M. C. Org. Lett. 2012, 14, 4318.
(10) For examples of slow addition/release of nucleophiles in cross-
coupling, see refs 8a−8e and: (a) Manolikakes, G.; Hernandez, C. M.;
Schade, M. A.; Metzger, A.; Knochel, P. J. Org. Chem. 2008, 73, 8422.
(b) Krasovskiy, A.; Duplais, C.; Lipshutz, B. H. J. Am. Chem. Soc. 2009,
131, 15592. (c) Vechorkin, O.; Barmaz, D.; Proust, V.; Hu, X. J. Am.
Chem. Soc. 2009, 131, 12078. (d) Cardellicchio, C.; Fiandanese, V.;
Marchese, G.; Ronzini, L. Tetrahedron Lett. 1987, 28, 2053. (e) Czaplik,
W. M.; Mayer, M.; Jacobi von Wangelin, A. Angew. Chem., Int. Ed. 2009,
48, 607. (f) Knapp, D. M.; Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc.
ACKNOWLEDGMENTS
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Financial support for this work was provided by the University of
Ottawa, the National Science and Engineering Research Council
of Canada (NSERC), and the Canada Research Chair program.
The Canadian Foundation for Innovation (CFI) and the Ontario
Ministry of Economic Development and Innovation are thanked
for essential infrastructure. J.M.M. and R.J.S. thank NSERC for
USRA and CGS-D awards, respectively.
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