J
B. Suchand, G. Satyanarayana
Paper
Synthesis
the crude material by silica gel column chromatography (PE/EtOAc)
furnished the product 3ci; yield: 71.0 mg (59%); red solid, m.p. 227–
230 °C; Rf (1c) = 1.0, Rf (3ci) = 0.30 (PE/EtOAc 80:20), UV detection.
Supporting Information
Supporting information for this article is available online at
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IR (MIR-ATR): 3061, 2937, 1711, 1692, 1618, 1469, 1285, 1181, 911,
715 cm–1
.
1H NMR (CDCl3, 400 MHz): δ =12.41 (s, 1 H, Ar–OH), 8.41 (d, J = 1.9 Hz,
1 H, ArH), 8.14 (d, J = 8.3 Hz, 1 H, ArH), 7.91 (dd, J = 8.3, 1.9 Hz, 1 H,
ArH), 7.81 (dd, J = 7.5, 1.2 Hz, 1 H, ArH), 7.69 (dd, J = 8.3, 8.3 Hz, 1 H,
ArH), 7.31 (dd, J = 8.3, 0.9 Hz, 1 H, ArH).
13C NMR (CDCl3, 100 MHz): δ =187.4 (s, C=O), 181.6 (s, C=O), 162.6 (s,
ArC), 137.7 (d, ArCH), 137.1 (d, ArCH), 134.3 (s, ArC), 133.2 (s, ArC),
132.2 (s, ArC), 129.9 (d, ArCH), 129.8 (s, ArC), 129.1 (d, ArCH), 124.6
(d, ArCH), 119.8 (d, ArCH), 115.9 (s, ArC).
References
(1) (a) Shi, Y. Q.; Fukai, T.; Sakagami, H.; Kuroda, J.; Miyaoka, R.;
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2847. (b) Gorelik, M. V. Chemistry of Anthraquinones and Their
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Waldmann, H. In Methods and Principles in Medicinal Chemistry:
HRMS (ESI+): m/z [M + H]+ calcd for [C14H879BrO3]+: 302.9651; found:
302.9662; [M
304.9648.
+
H]+ calcd for [C14H881BrO3]+: 304.9632; found:
Natural Products in Medicinal Chemistry;
V
o
l.
6
0
Hanessian, S., Ed.;
Wiley-VCH: Weinheim, 2014, 43. Reviews: (d) Kongsriprapan,
S.; Kuhakarn, C.; Deelertpaiboon, P.; Panthong, K.; Tuchinda, P.;
Pohmakotr, M.; Reutrakul, V. Pure Appl. Chem. 2012, 84, 1435.
(e) Babula, P.; Adam, V.; Havel, L.; Kizek, R. Curr. Pharm. Anal.
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ChemBioChem 2009, 10, 1392. (g) Kim, M. C.; Hwang, E.; Kim, T.;
Ham, J.; Kim, S. Y.; Kwon, H. C. J. Nat. Prod. 2014, 77, 2326.
(3) (a) Thomson, R. H. Naturally Occurring Quinones; Butterworths:
London, 1957, 309. (b) Fieser, L. F.; Fieser, M. Advanced Organic
Chemistry; Reinhold: New York, 1961, 845.
2-Fluoro-6-methoxyanthracene-9,10-dione (3da)
GP was carried out with ortho-iodoester 1d (112.0 mg, 0.40 mmol)
and aldehyde 2a (217.0 mg, 1.6 mmol) in the presence of Pd(OAc)2
(5.0 mg, 5 mol%), Ag2O (111.3 mg, 0.48 mmol), and TBHP (257.1 mg,
2.0 mmol) by allowinng the reaction mixture to stir at 120 °C for 14 h.
Progress of the reaction was monitored by TLC until the ortho-io-
doester 1d had completely reacted. Then the mixture was removed
from the oil bath and allowed to reach r.t. DCE (2 mL) and concd H2SO4
(1.0 mL) were added and the mixture was stirred at 60 °C for 2 h.
Progress of the product formation was monitored by TLC until the re-
action was complete. The mixture was quenched by the addition of aq
NaHCO3 and then extracted with CH2Cl2 (3 × 15 mL). The combined
organic layers were washed with brine, dried (Na2SO4), and filtered.
Evaporation of the solvent under reduced pressure and purification of
the crude material by silica gel column chromatography (PE/EtOAc)
furnished the product 3da; yield: 65.0 mg (63%); yellow viscous liq-
uid; Rf (1d) = 1.0, Rf (3da) = 0.30 (PE/EtOAc 95:05), UV detection.
(4) (a) Younos, C.; Rolland, A.; Fleurentin, J.; Lanhers, M. C.; Misslin,
R.; Mortier, F. Planta Med. 1990, 56, 430. (b) Koumaglo, K.;
Gbeassor, M.; Nikabu, O.; Souza, C.; Werner, W. Planta Med.
1992, 58, 533.
(5) (a) Lown, J. W. Pharmacol. Ther. 1993, 60, 185. (b) Scott, L. J.;
Figgitt, D. P. CNS Drugs 2004, 18, 379. (c) Galetta, S. L.;
Markowitz, C. CNS Drugs 2005, 19, 239. (d) Monterrey, I. G.;
Campiglia, P.; Carotenuto, A.; Califano, D.; Pisano, C.; Vesci, L.;
Lama, T.; Bertamino, A.; Sala, M.; Bosco, A. M.; Grieco, P.;
Novellino, E. J. Med. Chem. 2007, 50, 1787. (e) Castellano, S.;
Bertamino, A.; Monterrey, I. G.; Santoriello, M.; Grieco, P.;
Campiglia, P.; Sbardella, G.; Novellino, E. Tetrahedron Lett. 2008,
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K.; Lee, C. H. Bioorg. Med. Chem. 2008, 16, 1006. (g) Weyler, S.;
Baqi, Y.; Hillmann, P.; Kaulich, M.; Hunder, A. M.; Muller, I. A.;
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Vandegraaff, N.; Cox, S.; Coates, J. A. V.; Robertson, A. D. Bioorg.
Med. Chem. 2010, 18, 6442.
IR (MIR-ATR): 3071, 2928, 1711, 1689, 1622, 1462, 1285, 1181, 914,
705 cm–1
.
1H NMR (CDCl3, 400 MHz): δ = 8.30 (dd, J = 8.5, 5.1 Hz, 1 H, ArH), 8.22
(d, J = 8.8 Hz, 1 H, ArH), 7.90 (dd, J = 8.8, 2.4 Hz, 1 H, ArH), 7.70 (d, J =
2.4 Hz, 1 H, ArH), 7.43–7.38 (m, 1 H, ArH), 7.26–7.23 (m, 1 H, ArH),
3.97 (s, 3 H, OCH3).
13C NMR (CDCl3, 100 MHz): δ = 181.9 (s, C=O), 180.9 (s, C=O), 166.4 (s,
ArCF, JC,F = 260 Hz), 164.6 (s, ArC), 136.5 (s, ArC, JC,F = 8.7 Hz), 135.5 (s,
ArC), 130.5 (d, JC,F = 8.8 Hz, ArCH), 130.2 (s, JC,F = 2.9 Hz, ArC), 129.9 (d,
ArCH), 127.0 (s, ArC), 121.1 (d, ArCH), 120.9 (d, JC,F = 22.9 Hz, ArCH),
113.8 (d, JC,F = 22.7 Hz, ArCH), 110.2 (d, ArCH), 56.0 (q, CH3).
HRMS (ESI+): m/z [M + H]+ calcd for [C15H10FO3]+: 257.0608; found:
257.0606.
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Brasholz, M. Angew. Chem. Int. Ed. 2014, 53, 6558. (e) Petzold,
D.; König, B. Adv. Synth. Catal. 2018, 360, 626. (f) Li, B.; Fan, D.;
Yang, C.; Xia, W. Org. Biomol. Chem. 2016, 14, 5293. (g) Cui, L.;
Matusaki, Y.; Tada, N.; Miura, T.; Uno, B.; Itoh, A. Adv. Synth.
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(i) Yamaguchi, T.; Yamaguchi, E.; Itoh, A. Org. Lett. 2017, 19,
1282. (j) Yamaguchi, T.; Nobuta, T.; Tada, N.; Miura, T.;
Funding Information
We are grateful to the Department of Science and Technology-Science
and Engineering Research Board (DST-SERB) [NO.: SB/S1/OC-
39/2014], New Delhi, for the financial support. S.B. thanks MHRD for
the award of a research fellowship.
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–K