10.1002/adsc.201701579
Advanced Synthesis & Catalysis
[2] a) R. Hedge, P. Thimmaiah, M. C. Yerigeri, G.
Krishnegowda, K. N. Thimmaiah, P. J. Houghton,
Eur. J. Med. Chem. 2004, 39, 161-177. b) A. Pintr, A.
Sud, D. Sureshkumar, M. Klussmann, Angew. Chem.
Int. Ed. 2010, 49, 5004-5007.
[3] a) N. Suzuki, Y. Kazui, M. Kato, Y. Izawa,
Heterocycles 1981, 16, 2121-2124. b) N. Suzuki, Y.
Kazui, T. Tsukamoto, M. Kato, Y. Izawa, Bull. Chem.
Soc. Jap. 1983, 56, 1519-1521.
[4] J. Zhao, R. C. Larock, J. Org. Chem. 2007, 72, 583-588.
[5] For reviews of transition metal-catalyzed C-H
amination see: a) Y. Park, Y. Kim, S. Chang, Chem.
Rev. 2017, 117, 9247-9301. b) H. Kim, S. Chang,
ACS Catal. 2016, 6, 2341-2351. c) J. Jiao, K.
Murakami, K. Itami, ACS Catal. 2016, 6, 610-633. d)
T. A. Ramirez, B. G. Zhao, Y. A. Shi, Chem. Soc.
Rev. 2012, 41, 931-942. e) O. V. Zatolochnaya, V.
Gevorgyan, Nat. Chem. 2014, 6, 661-663.
[6] a) S. Choi, T. Chatterjee, W. J. Choi, Y. You, E. J. Cho,
ACS Catal. 2015, 5, 4796-4802. b) T. Sugahara, K.
Murakami, H. Yorimitsu, A. Osuka, Angew. Chem.
Int. Ed. 2014, 53, 9329-9333. c) L. L. Chng, J. Yang,
Y. F. Wei, J. Y. Ying, Chem. Commun. 2014, 50,
9049-9052. d) F. Pan, B. Wu, Z. J. Shi, Chem. Eur. J.
2016, 22, 6487-6490. e) Q. B. Jiang, D. D. Duan-Mu,
W. Zhong, H. Chen, H. Yan, Chem. Eur. J. 2013, 19,
1903-1907. f) S. W. Youn, J. H. Bihn, B. S. Kim, Org.
Lett. 2011, 13, 3738-3741. g) W. Zhou, Y. Liu, Y. Q.
Yanga, G. J. Deng, Chem. Commun. 2012, 48, 10678-
10680.
The reaction of 1a can also be carried out on gram
scale (5 mmol), with the desired product 2a obtained
in 70% yield (Scheme 4).
In summary, we have reported a transition-metal-
free method for synthesis of acridones through
intramolecular oxidative C–H amination. A series of
N–H and N-substituted acridone derivatives were
acquired in moderate to good yields in the presence
of KOt-Bu/DMSO.
Experimental Section
General procedure for intramolecular cyclization
A solution of 1a (49.1 mg, 0.2 mmol), KOt-Bu (67.2 mg,
0.6 mmol) in DMSO (2.0 mL) was stirred at room
temperature under an air atmosphere for 12 h. After the
completion of the reaction as shown by TLC, the crude
product was purified by flash chromatography to give 2a
as a yellow solid (36.5 mg, yield: 75%). m.p. 173–174 °C.
1H NMR (400 MHz, CDCl3) δ 8.46 (dd, J = 8.0, 1.6 Hz,
1H), 8.41 (d, J = 2.8 Hz, 1H), 7.69 (t, J = 7.8 Hz, 1H), 7.55
(dd, J = 9.2, 2.8 Hz, 1H), 7.45 (d, J = 8.8 Hz, 1H), 7.38 (d,
J = 9.2 Hz, 1H), 7.25 (t, J = 7.4 Hz, 1H), 3.81 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ 176.92, 142.27, 140.79, 134.11,
133.75, 127.66, 127.15, 126.69, 123.11, 122.22, 121.61,
116.60, 114.87, 33.79. HRMS (ESI) calculated for
C14H11NOCl (M+H)+ : 244.0524, found : 244.0518.
[7] a) Y. Monguchi, H. Okami, T. Ichikawa, K. Nozaki, T.
Maejima, Y. Oumi, Y. Sawama, H. Sajiki, Adv. Synth.
Catal. 2016, 358, 3145-3151. b) J. A. Jordan-Hore, C.
C. C. Johansson, M. Gulias, E. M. Beck, M. J. Gaunt,
J. Am. Chem. Soc. 2008, 130, 16184-16186. c) S. D.
Yang, B. J. Li, X. B. Wan, Z. J. Shi, J. Am. Chem. Soc.
2007, 129, 6066-6067. d) S. H. Cho, J. Yoon, S.
Chang. J. Am. Chem. Soc. 2011, 133, 5996-6005. e) T.
S. Mei, X. Wang, J. Q. Yu, J. Am. Chem. Soc. 2009,
131, 10806-10807. f) J. J. Neumann, S. Rakshit, T.
Dröge, F. Glorius, Angew. Chem. Int. Ed. 2009, 48,
6892-6895. g) M. Wasa, J. Q. Yu, J. Am. Chem. Soc.
2008, 130, 14058-14059.
Acknowledgements
This project was supported by the National Key Research and
Development Project of China (2016YFA0602900), the National
Natural Science Foundation of China (No. 21702236), the Doctor
Initiated Project of Guangdong Natural Science Foundation (No.
2016A030310459), the Key Project of Guangdong Natural
Science
Foundation
(2016A030311033),
STPGC
(201505041557046), and ISRTIPZC(2015-224). We are grateful
to Prof. Albert S. C. Chan at Sun Yat-sen University for guidance
and help.
[8] P. C. Huang, K. Parthasarathy, C. H. Cheng, Chem.
Eur. J. 2013, 19, 460-464.
[9] J. B. Huang, C. Q. Wan, M. F. Xu, Q. Zhu, Eur. J. Org.
Chem. 2013, 10, 1876-1880.
References
[1] a) C. S. Sepúlveda, C. C. García, M. L. Fascio, N. B.
D’Accorso, P. M. L. Docampo, R. F. Pellón, E. B.
Damonte, Antiviral Res. 2012, 93, 16-22. b) C. M.
Gao, Y. Y. Jiang, C. Y. Tan, X. Y. Zu, H. C. Liu, D.
R. Cao, Biorg. Med. Chem. 2008, 16, 8670-8675. c) R.
J. Harrison, A. P. Reszka, S. M. Haider, B.
Romagnoli, J. Morrell, M. A. Read, S. M. Gowan, C.
M. Incles, L. R. Kellandc, S. Neidle, Bioorg. Med.
Chem. Lett. 2004, 14, 5845-5849. d) J. Janočková, J.
Plšíková, J. Kášparková, V. Brabec, R. Jendželovský,
J. Mikeš, J. Kovaĺ, S. Hamuĺaková, P. Fedoročko, K.
Kuča, M. Kožurková, Eur. J. Pharm. Sci. 2015, 76,
192-202. e) K. Thimmaiah, A. G. Ugarkar, E. F.
Martis, M. S. Shaikh, E. C. Coutinho, M. C. Yergeri,
Nucleosides Nucleotides Nucleic Acids 2015, 34, 309-
331.
[10] J. W. Wen, S. Tang, F. Zhang, R. Y. Shi, A. W. Lei,
Org. Lett. 2017, 19, 94-97.
[11] W. D. Guerra, R. A. Rossi, A. B. Pierini, S. M. Barolo,
J. Org. Chem. 2015, 80, 928-941.
[12] W. T. Wei, Y. J. Cheng, Y. Hu. Y. Y. Chen, X. J.
Zhang, Y. Zou, M. Yan, Adv. Synth. Catal. 2015, 357,
3474-3478.
[13] Y. Suzuki, T. Toyota, A. Miyashita, M. Sato, Chem.
Pharm. Bull. 2006, 54, 1653-1658.
[14] Y. Y. Chen, Y. H. Chen, N. N. Zhang, L. M. Ye, X. J.
Zhang, M. Yan, Tetrahedron Lett. 2015, 56, 478-481.
[15] H. Q. Wang, Z. Wang, H. C. Huang, J. J. Tan, K. Xu,
Org. Lett. 2016, 18, 5680-5683.
[16] a) L. Gao, B. Chang, W. Z. Qiu, L. L. Wang, X. Z. Fu,
R. S. Yuan, Adv. Synth. Catal. 2016, 358, 1202-1207.
5
This article is protected by copyright. All rights reserved.