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Choudhury, A.; Mathieson, J.S.; Cronin, L.; Pardue, D.B.; Cundari,
T.R.; Mitrikas, G.; Sanakis, Y.; Stavropoulos, P. J. Am. Chem. Soc.
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and studies to determine how this design feature impacts
selectivity are currently underway.
1
2
3
4
5
6
7
8
In conclusion, we have developed two silver catalyst sys-
tems capable of promoting tunable, regioselective amina-
tion of C–H bonds in different chemical environments.
(2) For selected examples of directing groups used in conjunction
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t
Silver catalysts supported by Bubipy appear to prefer ami-
nation of the most electron-rich C–H bond, while silver
supported by a tpa ligand is more sensitive to the steric en-
vironment around the C–H bond, as well as the bond disso-
ciation energy. Preliminary mechanistic work indicates that
if radical intermediates are formed in either pathway, they
undergo rapid rebound, as no loss of stereochemical infor-
mation is noted.8 Computational studies are currently un-
derway to obtain a more detailed mechanistic picture of
both reaction pathways and gain a better understanding of
how the ligand identity affects the electronic and steric na-
ture of the purported silver nitrene intermediate. Another
exciting ongoing investigation is utilizing these initial re-
sults to parameterize features of both the silver-nitrenes and
the substrates to develop predictive models for site-
selectivity in complex substrates.
9
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ASSOCIATED CONTENT
Supporting Information
Experimental procedure and characterization is provided
for all new compounds. This material is available free of
Funding Sources
This research was supported by start-up funds provided by
the University of Wisconsin. The Varian INOVA 500 was
obtained with NSF Award #CHE-9629688. The Varian
UNITY 500 was obtained with NSF Award #CHE-8813550
and #CHE-9629688, as well as NIH Award #1–S10-
RR04981-01. The Varian Nanoprobe was obtained with
NIH Award #1–S10-RR04981-01.
(7) For recent selected examples, see: a) Collet, F.; Lescot, C.;
Dauban, P. Chem. Soc. Rev. 2011, 40, 1926. b) Harvey, M. E.; Mu-
saev, D. G.; Du Bois, J. J. Am. Chem. Soc. 2011, 133, 17207. c)
Paradine, S.M.; White, M.C. J. Am. Chem. Soc. 2012, 134, 2036.
(8) Rigoli, J.W.; Weatherly, C.D.; Alderson, J.M.; Vo, B.T.; Scho-
maker, J.M. J. Am. Chem. Soc. 2013, 135, 17238.
AUTHOR INFORMATION
Corresponding Author
(9) For selected examples of aminations mediated by silver catal-
ysis, see: a) Cui, Y.; He, C. J. Am. Chem. Soc. 2003, 125, 16202. b)
Cui, Y.; He, C. Angew. Chem. Int. Ed. 2004, 43, 4210. c) Li, Z.;
Capretto, D.A.; Rahaman, R.H.; He, C. Angew. Chem. Int. Ed.
2007, 46, 5184. d) Silver in Organic Chemistry. Harmata, M. ed.,
John Wiley & Sons: Hoboken, NJ 2010. e) Llaveria, J.; Beltran, A.;
Diaz-Requejo, M.M.; Matheu, M.I.; Castillon, S.; Pérez, P.J. Angew.
Chem. Int. Ed. 2010, 49, 7092. f) Fructos, M.R.; Trofimenko, S.;
Diaz-Requejo, M.M.; Pérez, P.J. J. Am. Chem. Soc. 2006, 128,
11784. g) Braga, A.A.C.; Maseras, F.; Urbano, J.; Caballero, A.;
Diaz-Requejo, M.M.; Pérez, P.J. Organometallics 2006, 25, 5292.
h) Maestre, L.; Sameera, W.M.C.; Dia-Requejo, M.M.; Maseras, F.;
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(10) For selected examples illustrating the various coordination
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CrystEngComm. 2008, 10, 1866. d) Hung-Low, F.; Renz, A.;
Klausmeyer, K.K. J. Chem. Cryst. 2009, 39, 438. e) Levason, W.;
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Author Contributions
‡These authors contributed equally.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENTS
The authors thank Ryan Van Hoveln for helpful discussions,
James Jirak for substrate synthesis, Charles Fry and Heike
Hofstetter for NMR assistance, and Martha Vestling for
assistance with mass spectrometry.
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