4
02
Synlett
Y. Fan et al.
Letter
Acknowledgment
(10) (a) Murugesan, D.; Kaiser, M.; White, K. L.; Norval, S.; Riley, J.;
Wyatt, P. G.; Charman, S. A.; Read, K. D.; Yeates, C.; Gilbert, I.
ChemMedChem 2013, 8, 1537. (b) Roy, B.; Hazra, S.; Mondal, B.;
Majumdar, K. C. Tetrahedron Lett. 2013, 54, 5979.
This work was financial supported by National High Technology Re-
search Development Program of China (863 Program,
2011AA10A207), National Natural Science Foundation of China
(11) (a) Jiang, B.; Li, Q. Y.; Tu, S. J.; Li, G. G. Org. Lett. 2012, 14, 5210.
(21472046, 21372079), Shanghai Pujiang Program (14PJD012) and
(
(
b) Alizadeh, A.; Zarei, A.; Rezvanian, A. Synthesis 2011, 497.
c) Pilipecz, M. V.; Mucsi, Z.; Nemes, P.; Scheiber, P. Heterocycles
the Fundamental Research Funds for the Central Universities. This
work was also partly supported by Australia DC Foundation.
2007, 71, 1919.
(12) Chen, N. Y.; Zou, M. M.; Tian, X.; Zhu, F. J.; Shao, X. S.; Li, Z. Eur. J.
Org. Chem. 2014, 6210.
Supporting Information
(13) (a) Mohammadizadeh, M. R.; Firoozi, N. Tetrahedron Lett. 2010,
5
1, 2467. (b) Mohammadizadeh, M. R.; Bahramzadeh, M.;
Taghavi, S. Z. Tetrahedron Lett. 2010, 51, 5807.
c) Mohammadizadeh, M. R.; Firoozi, N.; Aradeh, R. Helv. Chim.
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0034-1379617.
S
u
p
p
ortioIgnfrm oaitn
S
u
p
p
ortioIgnfrm oaitn
(
Acta 2011, 94, 410. (d) Mahdavinila, G. H.; Mohammadizadeh,
M. R.; Ariapour, N.; Alborz, M. Tetrahedron Lett. 2014, 55, 1967.
14) For the preparation of starting materials, see the Supporting
Information. All chiral compounds in this manuscript were
obtained as racemic mixtures.
References and Notes
(
(1) Rajesh, S. M.; Perumal, S.; Menéndez, J. C.; Yogeeswari, P.;
Sriram, D. Med. Chem. Commun. 2011, 2, 626.
(
15) Crystallographic data have been deposited with the accession
number CCDC 1029163 in the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax:
(2) (a) Lin, H.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2003, 42, 36.
(b) Galliford, C. V.; Scheidt, K. A. Angew. Chem. Int. Ed. 2007, 46,
8748. (c) Bencivenni, G.; Wu, L. Y.; Mazzanti, A.; Giannichi, B.;
+
44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk; website:
Pesciaioli, F.; Song, M. P.; Bartoli, G.; Melchiorre, P. Angew.
Chem. Int. Ed. 2009, 48, 7200.
www.ccdc.cam.ac.uk/conts/retrieving.html.
16) CCDC 1029164.
17) Typical Procedure for 2-{-[(6-Chloropyridin-3-yl)methyl]-5-
hydroxy-7-nitro-6-oxo-2,3,5,6-tetrahydro-1H-pyrrolo[1,2-
a]imidazol-5-yl}benzoic acid (3a)
(
(
(
3) (a) Jones, R. A.; Bean, G. P. The Chemistry of Pyrroles; Academic
Press: London, 1977, 1. (b) Sadek, B.; Limban, C.; Stecoza, C. E.;
Elz, S. Sci. Pharm. 2011, 79, 749. (c) Ma, F. F.; Gao, Y.; Qiao, H. L.;
Hu, X. J.; Chang, J. B. J. Thromb. Thrombolysis 2012, 33, 64.
The suspension of 1-[(6-chloropyridin-3-yl)methyl]-4a,9a-
dihydroxy-10-nitro-2,3,4a,9a-tetrahydroindeno[2′,1′:4,5]pyr-
rolo[1,2-a]imidazol-9(1H)-one (1a, 414 mg, 1 mmol) and NaIO4
(d) Zhang, S. L.; Liu, Y. J.; Zhao, Y. F.; Guo, Q. T.; Gong, P. Chin.
Chem. Lett. 2010, 21, 1071.
(
4) (a) Olmo, E. D.; Armas, M. G.; Ybarra, M. I.; López, J. L.; Oporto,
P.; Giménez, A.; Deharo, E.; Feliciano, A. S. Bioorg. Med. Chem.
Lett. 2003, 13, 2769. (b) Kümmerle, A. E.; Vieira, M. M.; Schmitt,
M.; Miranda, A. L. P.; Fraga, C. A. M.; Bourguignon, J. J.; Barreiro,
E. J. Bioorg. Med. Chem. Lett. 2009, 19, 4963. (c) Manivel, P.;
Khan, F. N.; Hatwar, V. R. Phosphorus, Sulfur Silicon Relat. Elem.
(
214 mg, 1 mmol) in H O (10 mL) was stirred at r.t. for 4 h. The
2
resulting solid 3a was isolated by filtration, washed with H O
2
and dried; light yellow solid; yield 395 mg (92%); mp 151–
1
1
52 °C. H NMR (400 MHz, DMSO-d ): δ = 13.11 (br s, 1 H), 8.47
6
(
d, J = 2.4 Hz, 1 H), 7.88 (dd, J = 8.4 Hz, J = 2.4 Hz, 1 H), 7.78 (d,
1 2
J = 7.6 Hz, 1 H), 7.60 (d, J = 8.4 Hz, 1 H), 7.57–7.51 (m, 1 H), 7.49–
2
2
010, 185, 1932. (d) Ramesha, A. R.; Roy, A. K. Synth. Commun.
001, 31, 2419.
7
4
3
.41 (m, 2 H), 5.36 (d, J = 16.0 Hz, 1 H), 5.10 (d, J = 16.0 Hz, 1 H),
.04 (td, J = 10.8 Hz, J = 3.6 Hz, 1 H), 3.90 (q, J = 10.8 Hz, 1 H),
1
2
(
5) (a) Andreani, A.; Granaiola, M.; Leoni, A.; Locatelli, A.; Morigi,
R.; Rambaldi, M.; Garaliene, V.; Farruggia, G.; Masotti, L. Bioorg.
Med. Chem. 2004, 12, 1121. (b) Andreani, A.; Granaiola, M.;
Leoni, A.; Locatelli, A.; Morigi, R.; Rambaldi, M.; Geraliene, V. J.
Med. Chem. 2002, 45, 2666. (c) Masamune, H.; Cheng, J. B.;
Cooper, K.; Eggler, J. F.; Marfat, A.; Marshall, S. C.; Shirley, J. T.;
Tickner, J. E.; Umland, J. P.; Vazquez, E. Bioorg. Med. Chem. Lett.
.54 (q, J = 10.8 Hz, 1 H), 3.27 (td, J = 9.6 Hz, J2 = 4.0 Hz, 1 H)
1
13
ppm. C NMR (100 MHz, DMSO-d ): δ =185.7, 170.2, 164.4,
6
149.6, 148.9, 139.0, 133.4, 133.2, 131.4, 129.6, 128.8, 128.7,
1
27.3, 124.3, 110.9, 85.6, 52.9, 48.5, 39.4 ppm. ESI-HRMS: m/z
35
+
calcd for C19H16N O Cl [M + H] : 431.0758; found: 431.0755;
m/z calcd for C19H16N O Cl [M
4
6
37
+
+ H] : 433.0729; found:
4
6
433.0747.
1995, 5, 1965. (d) Sun, L.; Tran, N.; Liang, C. X.; Hubbard, S.;
(
18) Typical Procedure for 1′-[(6-Chloropyridin-3-yl)methyl]-7′-
nitro-2′,3′-dihydro-3H-spiro{isobenzofuran-1,5′-pyr-
rolo[1,2-a]imidazole}-3,6′(1′H)-dione (4a)
Tang, F.; Lipson, K.; Schreck, R.; Zhou, Y.; McMahon, G.; Tang, C.
J. Med. Chem. 2000, 43, 2655.
(6) (a) Taniguchi, T.; Miyata, K.; Kubo, O. WO 2008096746, 2008.
The mixture of PTSA·H O (19.1 mg, 0.1 mmol) and 2-{1-[(6-
2
(b) Yao, W. Q.; Xu, M. Z.; Zhang, C. L.; Agrios, K.; Metcalf, B.;
chloropyridin-3-yl)methyl]-5-hydroxy-7-nitro-6-oxo-2,3,5,6-
tetrahydro-1H-pyrrolo[1,2-a]imidazol-5-yl}benzoic acid (3a,
Zhuo, J. C. WO 2006002349, 2006. (c) Bauer, V. J.; Kosley, R. W.
DE 2458176, 1975.
430 mg, 1 mmol) in MeOH (10 mL) was heated to 60 °C and
(
7) (a) Inubushi, Y.; Tsuda, Y.; Kontia, T.; Matsumoto, S. Chem.
Pharm. Bull. 1968, 16, 1014. (b) Kawanishi, K.; Uhara, Y.;
Hashimoto, Y. J. Nat. Prod. 1982, 45, 637.
stirred for 4 h. Product 4a precipitated and was separated from
the mixture by filtration; light yellow solid; yield 358 mg (87%);
1
mp 317–318 °C. H NMR (400 MHz, DMSO-d ): δ = 8.55 (d, J =
6
(8) (a) Su, S. K.; Li, C. J.; Jia, X. S.; Li, J. Chem. Eur. J. 2014, 20, 5905.
2
7
1
1
.4 Hz, 1 H), 8.04 (d, J = 8.0 Hz), 8.01 (dd, J = 8.4 Hz, J = 2.4 Hz),
1 2
(b) Cui, B. D.; Li, S. W.; Zuo, J.; Wu, Z. J.; Zhang, X. M.; Yuan, W. C.
.92 (t, J = 7.2 Hz, 1 H), 7.87 (d, J = 7.6 Hz, 1 H), 7.81 (t, J = 7.6 Hz,
H), 7.61 (d, J = 8.0 Hz, 1 H), 5.35 (d, J = 16.0 Hz, 1 H), 5.20 (d, J =
6.0 Hz, 1 H), 4.18–4.03 (m, 2 H), 3.67–3.57 (m, 1 H), 3.39–3.31
Tetrahedron 2014, 70, 1895. (c) Singh, H.; Sindhu, J.; Khurana, J.
M.; Sharma, C.; Aneja, K. R. Eur. J. Med. Chem. 2014, 77, 145.
9) (a) Gerbino, D. C.; Augner, D.; Slavov, N.; Schmalz, H. G. Org. Lett.
(
13
(m, 1 H) ppm. C NMR (100 MHz, DMSO-d ): δ = 180.1, 167.4,
6
2012, 14, 2338. (b) Tan, P. W.; Juwaini, N. A. B.; Seayad, J. Org.
1
1
64.6, 150.3, 149.9, 140.7, 139.9, 135.9, 132.5, 131.2, 127.3,
26.2, 124.8, 124.1, 111.4, 92.2, 54.4, 49.6, 40.6 ppm. ESI-HRMS:
Lett. 2013, 15, 5166. (c) Phan, D. H. T.; Kim, B.; Dong, V. M. J. Am.
Chem. Soc. 2009, 131, 15608.
©
Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 393–403