Organic Letters
Letter
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nature of two different fundamental catalytic operations,
namely oxidative addition of the palladium catalyst to Ar−Br
bonds in the presence of Ar−Cl bonds and preferential C−N
bond formation of primary urea nitrogen atoms. Finally, this
method utilizes a commercially available palladium precatalyst
and simple starting materials to provide direct and selective
access to a collection of complex benzimidazolones in a single
step.
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ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental procedures and data in addition to spectroscopic
data. This material is available free of charge via the Internet at
(9) (a) Benedí, C.; Bravo, F.; Uriz, P.; Fernan
́
dez, E.; Claver, C.;
AUTHOR INFORMATION
Castillon, S. Tetrahedron Lett. 2003, 44, 6073. (b) McLaughlin, M.;
́
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Palucki, M.; Davies, I. W. Org. Lett. 2006, 8, 3311. (c) Xu, X.-J.; Zong,
Y.-X. Tetrahedron Lett. 2007, 48, 129. (d) Zou, B.; Yuan, Q.; Ma, D.
Org. Lett. 2007, 9, 4291. (e) Barbero, N.; Carril, M.; SanMartin, R.;
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Corresponding Authors
Notes
The authors declare the following competing financial
interest(s): MIT has or has filed patents on the ligands/
precatalysts that are described in this paper from which S.L.B.
and former/current coworkers receive royalty payments.
ACKNOWLEDGMENTS
■
Financial support for this project was provided by the National
Institutes of Health under award numbers GM58160 (S.L.B.)
and GM099817 (N.T.J.). The content is the sole responsibility
of the authors and is not necessarily representative of the views
held by the NIH. Student support was generously provided by
Lanxess (J.B.E.) and the Amgen-UROP Scholars Program at
MIT (N.E.S.T.). We thank Dr. Aaron Sather (MIT) for help in
preparing this manuscript.
(14) Bruno, N. C.; Tudge, M. T.; Buchwald, S. L. Chem. Sci. 2013, 4,
916.
(15) When 4-methoxyphenylurea was used as a substrate under the
described conditions, a low yield of the desired benzimidazolone was
obtained and decomposition products (p-anisidine and 4-methoxy-
phenylisocyanate) were observed by GCMS.
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