Organic Letters
Letter
Chem., Int. Ed. 2013, 52, 6043. (e) Shang, M.; Sun, S.-Z.; Dai, H.-X.;
Yu, J.-Q. J. Am. Chem. Soc. 2014, 136, 3354. (f) Xu, H.; Qiao, X.; Yang,
S.; Shen, Z. J. Org. Chem. 2014, 79, 4414. (g) Kim, H.; Shin, K.;
Chang, S. J. Am. Chem. Soc. 2014, 136, 5904.
ready modifiable nature of the N-phthalimide moiety, we
believe the current method is synthetically viable.
In summary, we have shown a Ru(II)-catalyzed MPS-RDG
enabled o-C−H imidation of benzoic acid derivatives with N-
tosyloxyphthalimide. The current method exhibits major
outcomes: the participation of a broad substrate scope
including heteroarenes and tolerance of a wide array of
functional groups, the facile reactivity of o-substituted
compounds for the efficient production of the o-C−N bond,
the occurrence of challenging o-di-imidations, the realization of
sequential o-C−N and o-C−C bonds, the easy recovery of the
MPS group from the products, and the ready modification of
the phthalimide moiety leading to anilines. With these benefits,
we believe this method will find broad synthetic application.
(5) For the transition-metal catalyzed amination/amidation of
(hetero)arenes with electrophilic aminating reagents and the use of
N-halo derivatives, see: (a) Ng, K.-H.; Zhou, Z.; Yu, W.-Y. Org. Lett.
2011, 14, 272. (b) Grohmann, C.; Wang, H.; Glorius, F. Org. Lett.
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2013, 49, 7031. (d) Ng, F.-N.; Zhou, Z.; Yu, W.-Y. Chem.−Eur. J.
2014, 20, 4474. The use of NFSI, see: (e) Sun, K.; Li, Y.; Xiong, T.;
Zhang, J.; Zhang, Q. J. Am. Chem. Soc. 2011, 133, 1694. (f) Tang, R.-J.;
Luo, C.-P.; Yang, L.; Li, C.-J. Adv. Synth. Catal. 2013, 355, 869. The
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Am. Chem. Soc. 2010, 132, 3676. (i) Yoo, E. J.; Ma, S.; Mei, T.-S.;
Chan, K. S. L.; Yu, J.-Q. J. Am. Chem. Soc. 2011, 133, 7652. (j) Zhu, D.;
Yang, G.; He, J.; Chu, L.; Chen, G.; Gong, W.; Chen, K.; Eastgate, M.
D.; Yu, J.-Q. Angew. Chem. Int., Ed. 2015, 54, 2497. (k) Grohmann, C.;
Wang, H.-G.; Glorius, F. Org. Lett. 2013, 15, 3014. (l) Yu, S.; Wan, B.;
Li, X. Org. Lett. 2013, 15, 3706. (m) Zhou, B.; Du, J.; Yang, Y.; Feng,
H.; Li, Y. Org. Lett. 2014, 16, 592. (n) Patel, P.; Chang, S. Org. Lett.
2014, 16, 3328. (o) Allen, L. J.; Cabrera, P. J.; Lee, M.; Sanford, M. S.
J. Am. Chem. Soc. 2014, 136, 5607. (p) Du, J.; Yang, Y.; Feng, H.; Li,
Y.; Zhou, B. Chem.−Eur. J. 2014, 20, 5727. The use of sulfonyl azides,
see: (q) Kim, J. K.; Park, S. H.; Ryu, J.; Cho, S. H.; Kim, S. H.; Chang,
S. J. Am. Chem. Soc. 2012, 134, 9110. (r) Ryu, J.; Shin, K.; Park, S. H.;
Kim, J. Y.; Chang, S. Angew. Chem., Int. Ed. 2012, 51, 9904. (s) Kim, J.
W.; Chang, S. Angew. Chem., Int. Ed. 2014, 53, 2203 and references
cited therein.
ASSOCIATED CONTENT
* Supporting Information
■
S
Detailed experimental procedures and spectra. This material is
AUTHOR INFORMATION
Corresponding Author
■
Author Contributions
†M.R.Y. and M.S. contributed equally.
Notes
(6) Removable DG: (a) Rousseau, G.; Breit, B. Angew. Chem., Int. Ed.
2011, 50, 2450. (b) Wang, C.; Huang, Y. Synlett 2013, 24, 145.
(c) Zhang, F.; Spring, D. R. Chem. Soc. Rev. 2014, 43, 6906.
(7) (a) Yadav, M. R.; Rit, R. K.; Sahoo, A. K. Org. Lett. 2013, 15,
1638. (b) Kim, J. Y.; Kim, J. W.; Chang, S. Chem.Eur. J. 2013, 19,
7328. (c) Bhanuchandra, M.; Yadav, M. R.; Rit, R. K.; Kuram, M. R.;
Sahoo, A. K. Chem. Commun. 2013, 49, 5225. (d) Thirunavukkarasu,
V. S.; Raghuvanshi, K.; Ackermann, L. Org. Lett. 2013, 15, 3286.
(e) Zhen, Q.-Z.; Liang, Y.-F.; Qin, C.; Jiao, N. Chem. Commun. 2013,
49, 5654. (f) Pan, C. D.; Abdukader, A.; Han, J.; Cheng, Y. X.; Zhu, C.
J. Chem.Eur. J. 2014, 20, 3606.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank SERB, INDIA, and ACRHEM for financial support.
M.R.Y., M.S., E.R., and K.G. thank CSIR, India for a fellowship
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