ACS Catalysis
Research Article
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2014, 20, 11496−11504.
Finally, with a combination of experimental KIE studies and
computational mechanistic analyses, we have revealed that the
ortho-deuteration of primary sulfonamides with catalyst 16
proceeds similarly to analogous HIE processes employing
catalyst 6.7c Further, we have analyzed the complexation modes
and C−H activation pathways associated with labeling
Celecoxib, 21 using catalysts 6 and 16. As a result, we can
now propose that the pyrazole chemoselectivity of catalyst 6 is
driven by the substrate complexation event, whereas the
sulfonamide selectivity imparted by catalyst 16 is influenced by
the energetics of both complexation and subsequent C−H
activation. This, once again, emphasizes the importance of
considering the interactions of catalyst and substrate in acute
detail aligned to the overall C−H activation process, as the
observed activities and chemoselectivities may be as a result of
more than one contributing factor.
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Work is ongoing within our laboratories to extend the
application of these emerging iridium catalyst species to a more
expansive array of substrate classes, including sulfonamide-
based molecular architectures, as well as to alternative C−H
activation processes in a wider sense.
ASSOCIATED CONTENT
* Supporting Information
The following file is available free of charge on the ACS
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S
Details of all experimental procedures and DFT
calculation, including optimized Cartesian coordinates
(9) In contrast, C-H activation with secondary sulfonamides has been
studied more thoroughly. For examples of palladium-catalyzed C-H
activation using secondary sulfonamides, see for example: (a) Dai, H.-
X.; Stepan, A. F.; Plummer, M. S.; Zhang, Y.-H.; Yu, J.-Q. J. Am. Chem.
Soc. 2011, 133, 7222−7228. (b) Miura, M.; Tsuda, T.; Satoh, T.; Pivsa-
Art, S.; Nomura, M. J. Org. Chem. 1998, 63, 5211−5215.
(10) For examples of rhodium-catalyzed C-H activation using
secondary sulfonamides, see for example: (a) Pham, M. V.; Ye, B.;
Cramer, N. Angew. Chem., Int. Ed. 2012, 51, 10610−10614. (b) Zhu,
C.; Xie, W.; Falck, J. R. Chem.Eur. J. 2011, 17, 12591−12595. (c) Li,
X.; Gong, X.; Zhao, M.; Song, G.; Deng, J.; Li, X. Org. Lett. 2011, 13,
5808−5811.
AUTHOR INFORMATION
Corresponding Authors
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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(11) Hesk, D.; Das, P. R.; Evans, B. J. Label. Compd. Radiopharm.
1995, 36, 497−502.
The authors would like to thank the Carnegie Trust for the
Universities of Scotland (to M.R.) for funding. Mass
spectrometry data were acquired at the EPSRC UK National
Mass Spectrometry Facility at Swansea University.
(12) Ellames, G. J.; Gibson, J. S.; Herbert, J. M.; McNeill, A. H.
Tetrahedron 2001, 57, 9487−9497.
(13) Crabtree, R. H.; Felkin, H.; Morris, G. E. J. Organomet. Chem.
1977, 144, 205−215.
(14) McAuley, B.; Hickey, M. J.; Kingston, L. P.; Jones, J. R.; Lockley,
W. J. S.; Mather, A. N.; Spink, E.; Thompson, S. P.; Wilkinson, D. J. J.
Label. Compd. Radiopharm. 2003, 46, 1191−1204.
(15) Cross, P. W. C.; Ellames, G. J.; Gibson, J. S.; Herbert, J. M.;
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(16) Shu, A. Y. L.; Chen, W.; Heys, J. R. J. Organomet. Chem. 1996,
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(17) Catalyst 6 is available commercially from Strem Chemicals, Ltd.
(18) Kelly, R. A., III; Clavier, H.; Giudice, S.; Scott, S. M.; Stevens, E.
D.; Bordner, J.; Samardjiev, I.; Hoff, C. D.; Cavallo, L.; Nolan, S. P.
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