ORGANIC
LETTERS
XXXX
Vol. XX, No. XX
000–000
Rhodium(III)-Catalyzed CÀH Activation
and Amidation of Arenes Using
N‑Arenesulfonated Imides
as Amidating Reagents
Songjie Yu, Boshun Wan,* and Xingwei Li*
Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian 116023, China
xwli@dicp.ac.cn; bswan@dicp.ac.cn
Received June 4, 2013
ABSTRACT
Rhodium(III)-catalyzed CÀH activationÀamidation of arenes bearing chelating groups has been achieved using N-arenesulfonated imides as efficient
amidating reagents without using any base additive. Pyridine, oxime, and pyrimidine proved to be viable directing groups.
CÀN bonds are a key linkage in organics, pharmaceu-
ticals, and materials. Various methods for catalytic CÀN
couplings such as the BuchwaldÀHartwig coupling, the
Ullman coupling, and the ChanÀLam coupling have been
developed.1 These systems utilize aryl halides/tosylates or
boronic acids as a coupling partner. With increasing
interest in catalytic activation of CÀH bonds,2 it is im-
portant to take advantage of the ubiquity of CÀH bonds
for CÀN coupling. Hence considerable studies on the
amination of CÀH bonds have been performed using
Pd3 and Cu4 catalysts under oxidative conditions.
Alternatively, there have been increasing studies using
internaloxidizing NÀO and NÀhalogen groups for overall
redox-neutral amination reactions.5 Despite the progress,
because of the structural diversity and specificity of arene
substrates, it is necessary to develop amination reactions
catalyzed by other transitional metals. In this context,
Rh(III) complexes have been successfully employed as
(1) (a) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534. (b) Wolfe, J. P.;
Wagaw, S.; Marcoux, J.-F.; Buchwald, S. L. Acc. Chem. Res. 1998, 31,
805. (c) Surry, D. S.; Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47,
6338. (d) Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed. 2009, 48,
6954. (d) Armstrong, A.; Collins, J. C. Angew. Chem., Int. Ed. 2010, 49,
2286. (e) Collet, F.; Dodd, R. H.; Dauban, P. Chem. Commun. 2009,
5061. (f) Muller, P.; Fruit, C. Chem. Rev. 2003, 103, 2905. (h) Qiao, J.-X.;
Lam, P. Y. S. Synthesis 2011, 6, 829. (i) Zhang, M. Synthesis 2011, 21,
3408. (j) Mei, T.-S.; Kou, L.; Ma, S.; Engle, K. M.; Yu, J.-Q. Synthesis
2012, 44, 1778.
(2) (a) Giri, R.; Shi, B.-F.; Engle, K. M.; Maugel, N.; Yu, J.-Q. Chem.
Soc. Rev. 2009, 38, 3242. (b) Lyons, T. W.; Sanford, M. S. Chem. Rev.
2010, 110, 1147. (c) Ackermann, L. Chem. Rev. 2011, 111, 1315. (d) Xu,
L.-M.; Yang, Z.; Shi, Z.-J. Chem. Soc. Rev. 2010, 39, 712. (e) Yeung,
C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215. (f) Wencel-Delord, J.;
Droge, T.; Liu, F.; Glorius, F. Chem. Soc. Rev. 2011, 40, 4740. (g) Cho,
S. H.; Kim, J. Y.; Kwak, J.; Chang, S. Chem. Soc. Rev. 2011, 40, 5068.
(3) (a) Tsang, W. C. P.; Zheng, N.; Buchwald, S. L. J. Am. Chem. Soc.
2005, 127, 14560. (b) Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2008, 130,
14058. (c) Mei, T.-S.; Wang, X.; Yu, J.-Q. J. Am. Chem. Soc. 2009, 131,
10806. (d) Neumann, J.; Rakshit, S.; Droge, T.; Glorius, F. Angew.
Chem., Int. Ed. 2009, 48, 6892. (e) Martinez, C.; Muniz, K. Angew.
Chem., Int. Ed. 2012, 51, 7031. (f) Xiao, B.; Gong, T.-J.; Xu, J.; Liu, Z.-J.;
Liu, L. J. Am. Chem. Soc. 2011, 133, 1466. (g) Shrestha, R.; Mukherjee,
P.; Tan, Y.-C.; Litman, Z. C.; Hartwig, J. F. J. Am. Chem. Soc. 2013,
135, 8480. (h) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M. J. Am. Chem. Soc.
2006, 128, 9048. (i) Liu, G.-S.; Stahl, S. S. J. Am. Chem. Soc. 2007, 129,
6328.
(4) (a) Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett.
2011, 13, 2860. (b) Monguchi, D.; Fujiwara, T.; Furukawa, H.; Mori, A.
Org. Lett. 2009, 11, 1607. (c) Brasche, G.; Buchwald, S. L. Angew.
Chem., Int. Ed. 2008, 47, 1932. (d) Wang, H.; Wang, Y.; Peng, C.; Zhang,
J.; Zhu, Q. J. Am. Chem. Soc. 2010, 132, 13217. (e) Cho, S. H.; Yoon, J.;
Chang, S. J. Am. Chem. Soc. 2011, 133, 5996. (f) Lu, J.; Jin, Y.; Liu, H.;
Jiang, Y.; Fu, H. Org. Lett. 2011, 13, 3694. (g) John, A.; Nicholas, K. M.
J. Org. Chem. 2011, 76, 4158. (h) Wang, Q.; Schreiber, S. L. Org. Lett.
2009, 11, 5178.
(5) (a) Tan, Y.-C.; Hartwig, J. F. J. Am. Chem. Soc. 2010, 132, 3676.
(b) Yoo, E. J.; Ma, S.; Mei, T.-S.; Chan, K. S. L.; Yu, J.-Q. J. Am. Chem.
Soc. 2011, 133, 7652. (c) Ng, K.-H.; Chan, A. S. C.; Yu, W.-Y. J. Am.
Chem. Soc. 2010, 132, 12862. (d) Kawano, T.; Hirano, K.; Satoh, T.;
Miura, M. J. Am. Chem. Soc. 2010, 132, 6900. (e) Liu, X.-Y.; Gao, P.;
Shen, Y.-W.; Liang, Y.-M. Org. Lett. 2011, 13, 4196. (f) Xiao, Q.; Tian,
L.-M.; Tan, R.-C.; Xia, Y.; Qiu, D.; Zhang, Y.; Wang, J.-B. Org. Lett.
2012, 14, 4230.
r
10.1021/ol401569u
XXXX American Chemical Society