BULLETIN OF THE
Article
2-Arylindoles as a New Entry to 2-Aminobenzophenones
KOREAN CHEMICAL SOCIETY
G. D. Hartman, C. Tang, J. Ballard, Y. Kuo,
T. Prueksaritanont, C. E. Nuss, S. M. Doran, S. V. Fox,
S. L. Garson, R. L. Kraus, Y. Li, M. J. Marino,
V. K. Graufelds, V. N. Uebele, J. J. Renger, ACS Med. Chem.
Lett. 2010, 1, 75; (f ) Y. Yan, Z. Wang, Chem. Commun.
2011, 47, 9513; (g) R. K. Singh, D. N. Prasad,
T. R. Bhardwaj, Med. Chem. Res. 2013, 22, 5901;
(h) D.-S. Su, J. L. Lim, E. Tinney, B.-L. Wan, K. L. Murphy,
D. R. Reiss, C. M. Harrell, S. S. O’Malley, R. W. Ransom,
R. S. L. Chang, D. J. Pettibone, J. Yu, C. Tang,
T. Prueksaritanont, R. M. Freidinger, M. G. Bock,
N. J. Anthony, J. Med. Chem. 2008, 51, 3946;
(i) D. A. Walsh, M. C. Sleevi, L. F. Sancilio, J. Med. Chem.
1984, 27, 1317; (j) J. Sakowski, I. Sattler, M. Schlitzera,
Bioorg. Med. Chem. 2002, 10, 233; (k) R. Romagnoli,
P. G. Baraldi, T. Sarkar, M. D. Carrion, C. L. Cara, O. Cruz-
Lopez, D. Preti, M. A. Tabrizi, M. Tolomeo, S. Grimaudo,
A. D. Cristina, N. Zonta, J. Balzarini, A. Brancale, H.-
P. Hsieh, E. Hamel, J. Med. Chem. 2008, 51, 1464.
Me
Me
Me
O
OH
Ph
O2
Ph
Ph
N
N
N
H
II'
1q
I'
O
O
Me
O
Me
O
O
Ph
N
N
H
N
H
Ph
Ph
H
VIII
IX
5 (36%)
Scheme 4. Formation of 5 from 1q.
J = 8.4 Hz, 1H), 7.29 (t, J = 8.4 Hz, 1H), 7.42–7.49 (m,
3H), 7.50–7.56 (m, 1H), 7.61–7.67 (m, 2H); 13C NMR
(CDCl3, 75 MHz) δ 115.48, 116.96, 118.12, 128.05,
129.09, 131.01, 134.21, 134.57, 140.06, 150.89, 199.07;
ESIMS m/z 198 [M++H].
2-Amino-5-chlorobenzophenone (2b): 59%; yellow
2o
1
ꢀ
ꢀ
2. For synthesis of 2-aminobenzophenones, see:(a) D. A. Walsh,
Synthesis 1980, 677; (b) I. Ivanov, S. Nikolova, S. Statkova-
Abeghe, Synth. Commun. 2006, 36, 1405; (c) C. Peifer,
K. Kinkel, M. Abadleh, D. Schollmeyer, S. Laufer, J. Med.
Chem. 2007, 50, 1213; (d) W. Hu, Z. Guo, F. Chu, A. Bai,
X. Yi, G. Cheng, J. Li, Bioorg. Med. Chem. 2003, 11, 1153;
(e) M. Laube, C. Tondera, S. K. Sharma, N. Bechmann, F.-
J. Pietzsch, A. Pigorsch, M. Kockerling, F. Wuest,
J. Pietzsch, T. Kniess, RSC Adv. 2014, 4, 38726; (f )
K. Prasad, G. T. Lee, A. Chaudhary, M. J. Girgis,
J. W. Streemke, O. Repic, Org. Process Res. Dev. 2003, 7,
723; (g) T. Sugasawa, T. Toyoda, M. Adachi, K. Sasakura,
J. Am. Chem. Soc. 1978, 100, 4842; (h) P. Fang, M. Li,
H. Ge, J. Am. Chem. Soc. 2010, 132, 11898; (i) Y. Wu,
B. Li, F. Mao, X. Li, F. Y. Kwong, Org. Lett. 2011, 13,
3258; (j) C. Li, L. Wang, P. Li, W. Zhou, Chem. Eur. J.
2011, 17, 10208; (k) C.-W. Chan, Z. Zhou, W.-Y. Yu, Adv.
Synth. Catal. 2011, 353, 2999; (l) Y. Yuan, D. Chen,
X. Wang, Adv. Synth. Catal. 2011, 353, 3373; (m) Y. Wu,
P. Y. Choy, F. Mao, F. Y. Kwong, Chem. Commun. 2013,
49, 689; (n) Y. Wu, L.-J. Feng, X. Lu, F. Y. Kwong, H.-
B. Luo, Chem. Commun. 2014, 50, 15352; (o) J. Chen,
L. Ye, W. Su, Org. Biomol. Chem. 2014, 12, 8204;
(p) J. Chen, J. Li, W. Su, Molecules 2014, 19, 6439;
(q) W. Su, C. Jin, J. Chem. Res. 2004, 611; (r) C. Mateos,
J. A. Rincon, J. Villanueva, Tetrahedron Lett. 2013, 54,
2226; (s) M. H. Bolli, J. Marfurt, C. Grisostomi, C. Boss,
C. Binkert, P. Hess, A. Treiber, E. Thorin, K. Morrison,
S. Buchmann, D. Bur, H. Ramuz, M. Clozel, W. Fischli,
T. Weller, J. Med. Chem. 2004, 47, 2776; (t) M. V. Khedkar,
P. J. Tambade, Z. S. Qureshi, B. M. Bhanage, Eur. J. Org.
Chem. 2010, 6981; (u) A. Ahlburg, A. T. Lindhardt,
R. H. Taaning, A. E. Modvig, T. Skrydstrup, J. Org. Chem.
2013, 78, 10310; (v) M. Cai, J. Peng, W. Hao, G. Ding,
Green Chem. 2011, 13, 190.
solid, m.p. 94–96 C (lit. 97–98 C); H NMR (CDCl3,
300 MHz) δ 6.08 (s, 2H), 6.69 (d, J = 8.7 Hz, 1H), 7.24
(dd, J = 8.7, 2.7 Hz, 1H), 7.41 (d, J = 2.7 Hz, 1H),
7.44–7.52 (m, 2H), 7.53–7.60 (m, 1H), 7.61–7.67 (m, 2H);
13C NMR (CDCl3, 150 MHz) δ 118.43, 118.75, 119.91,
128.29, 129.06, 131.48, 133.21, 134.14, 139.27, 149.33,
197.97; ESIMS m/z 232 [M++H], 234 [M++H + 2].
2-Amino-5-methylbenzophenone (2c): 55%; yellow
solid, m.p. 62–64 ꢀC (lit.2q 59 ꢀC); 1H NMR (CDCl3,
300 MHz) δ 2.18 (s, 3H), 5.92 (s, 2H), 6.67 (d, J = 8.4 Hz,
1H), 7.13 (d, J = 8.4 Hz, 1H), 7.23 (s, 1H), 7.42–7.56 (m,
3H), 7.62–7.67 (m, 2H); 13C NMR (CDCl3, 150 MHz) δ
20.29, 117.10, 118.20, 124.57, 128.04, 129.09, 130.97,
134.03, 135.36, 140.16, 148.73, 199.03; ESIMS m/z
212 [M++H].
Acknowledgments. This work was supported by the
National Research Foundation of Korea (NRF) grant
funded by the Korea government (MSIP) (NRF-
2015R1A4A1041036). Spectroscopic data were obtained
from the Korea Basic Science Institute, Gwangju branch.
Supporting Information. Additional supporting informa-
tion is available in the online version of this article.
References
1. For synthetic usefulness of 2-aminobenzophenones, see:
(a) M. Anzini, S. Valenti, C. Braile, A. Cappelli, S. Vomero,
S. Alcaro, F. Ortuso, L. Marinelli, V. Limongelli,
E. Novellino, L. Betti, G. Giannaccini, A. Lucacchini,
S. Daniele, C. Martini, C. Ghelardini, L. D. C. Mannelli,
G. Giorgi, M. P. Mascia, G. Biggio, J. Med. Chem. 2011, 54,
5694; (b) C.-S. Jia, Z. Zhang, S.-J. Tu, G.-W. Wang, Org.
Biomol. Chem. 2006, 4, 104; (c) J. Wu, H.-G. Xia, K. Gao,
Org. Biomol. Chem. 2006, 4, 126; (d) K. Kobayashi,
S. Fujita, S. Fukamachi, H. Konishi, Synthesis 2009, 3378;
(e) J. C. Barrow, K. E. Rittle, T. S. Reger, Z.-Q. Yang,
P. Bondiskey, G. B. McGaughey, M. G. Bock,
3. S. Kumar, V. Rathore, A. Verma, C. D. Prasad, A. Kumar,
A. Yadav, S. Jana, M. Sattar, Meenakshi, S. Kumar, Org.
Lett. 2015, 17, 82.
4. For some selected synthesis of 3-aryl-3-hydroxyoxindoles,
see:(a) P. Y. Toullec, R. B. C. Jagt, J. G. de Vries,
B. L. Feringa, A. J. Minnaard, Org. Lett. 2006, 8, 2715;
(b) Z.-K. Xiao, H.-Y. Yin, L.-X. Shao, Org. Lett. 2013, 15,
Bull. Korean Chem. Soc. 2016, Vol. 37, 893–897
© 2016 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
896