Organic Letters
Letter
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yield, with highly attenuated reactivity in the absence of 7. Finally
anisole selectively brominated at the para position to give 31 in
excellent yields (91% at 3 h) with little to no reaction in the
absence of a catalyst.
In summary, we have developed a practical, inexpensive, and
highly reactive Lewis basic catalytic system to promote the
chlorination, and, more generally, halogenation of diverse arenes
and heterocycles, with many examples validated on gram scales.
The dependence of this chemistry on the presence of catalysts
opens up the possibility to design next generation phosphine
sulfide catalysts that effect enantio- or regioselective chlorina-
tions.
(25) Du, Z.-J.; Gao, L.-X.; Lin, Y.-J.; Han, F.-S. ChemCatChem 2014, 6,
123.
(26) Tian, Q.; Chen, X.; Liu, W.; Wang, Z.; Shi, S.; Kuang, C. Org.
Biomol. Chem. 2013, 11, 7830.
(27) Rodriguez, R. A.; Pan, C.-M.; Yabe, Y.; Kawamata, Y.; Eastgate, M.
D.; Baran, P. S. J. Am. Chem. Soc. 2014, 136, 6908.
(28) Denmark, S. E.; Beutner, G. L. Angew. Chem., Int. Ed. 2008, 47,
1560.
(29) Denmark, S. E.; Kuester, W. E.; Burk, M. T. Angew. Chem., Int. Ed.
2012, 51, 10938.
(30) Denmark, S. E.; Burk, M. T. Proc. Natl. Acad. Sci. U.S.A. 2010, 107,
20655.
(31) Snyder, S. A.; Treitler, D. S.; Brucks, A. P. J. Am. Chem. Soc. 2010,
132, 14303.
ASSOCIATED CONTENT
* Supporting Information
Experimental procedures and analytical data for all new
compounds, including 1H and 13C NMR spectra. This material
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S
AUTHOR INFORMATION
Corresponding Author
■
Author Contributions
†S.M.M. and C.J.N. contributed equally.
Notes
(32) Ke, Z.; Tan, C.; Chen, F.; Yeung, Y. J. Am. Chem. Soc. 2014, 136,
5627.
(33) Tay, D. W.; Leung, G. Y. C.; Yeung, Y.-Y. Angew. Chem., Int. Ed.
2014, 53, 5161.
(34) Tay, D. W.; Tsoi, I. T.; Er, J. C.; Leung, G. Y. C.; Yeung, Y.-Y. Org.
Lett. 2013, 15, 1310.
(35) Cohen, M. S.; Zhang, C.; Shokat, K. M.; Taunton, J. Science 2005,
308, 1318.
(36) Calderwood, D. J.; Johnston, D. N.; Rafferty, P.; Twigger, H. L.;
Munschauer, R.; Arnold, L. Pyrrolo[2,3D]pyrimidines and Their Uses
as Tyrosine kinase Inhibitors. WO 98/41525, 1998.
(37) Welsch, M. E.; Snyder, S. A; Stockwell, B. R. Curr. Opin. Chem.
Biol. 2010, 14, 347.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank our colleagues in the department of chemistry and
biochemistry at SDSU, particularly Professor Douglas Grotjahn
for insightful discussion and use of chemicals as well as Josh
Swider for technical support. This work was supported by startup
funds from SDSU.
(38) Ashtekar, K. D.; Marzijarani, N. S.; Jaganathan, A.; Holmes, D.;
Jackson, J. E.; Borhan, B. J. Am. Chem. Soc. 2014, 136, 13355.
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