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Synlett 2010(2): 276-278  
DOI: 10.1055/s-0029-1218560
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Synthesis of Functionalized Anthraquinones by Domino Twofold Heck-6π-Electrocyclization Reactions of 2,3-Dibromonaphthoquinone

Munawar Hussaina, Dhafer Saber Zinada, Ghazwan Ali Salmana, Muhammad Sharifa, Alexander Villingera, Peter Langer*a,b
a Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
Fax: +49(381)498 6412; e-Mail: peter.langer@uni-rostock.de;
b Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany
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Publication History

Received 5 October 2009
Publication Date:
09 December 2009 (online)

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Abstract

Functionalized anthraquinones were prepared by domino ‘twofold Heck-6π-electrocyclization’ reactions of 2,3-dibromo­naphthoquinone.

Key Words

catalysis - palladium - Heck reaction - electrocyclization - naphtoquinones

    References and Notes

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General Procedure for the Synthesis of 3a-q and 4a-q
In a pressure tube (glass bomb) a suspension of Pd(OAc)2 (12 mg, 0.05 mmol, 5 mol%) and XPhos (48 mg, 0.10 mmol) in DMF (5 mL) was purged with argon and stirred at 20 ˚C to give a yellowish or brownish clear solution. To the stirred solution were added 1 (316 mg, 1.0 mmol), Et3N (1.1 mL, 8.0 mmol), and the alkene 2a-q (2.5 equiv). The reaction mixture was stirred at 90 ˚C (for 3a-q) or 110 ˚C (for 4a-q) for 8 h. The solution was cooled to 20 ˚C, poured into H2O and CH2Cl2 (25 mL each), and the organic and the aqueous layer were separated. The latter was extracted with CH2Cl2 (3 × 25 mL). The combined organic layers were washed with H2O (3 × 20 mL), dried (Na2SO4), concentrated in vacuo, and the residue was purified by chromatography (flash silica gel, heptanes-EtOAc) to give 3a-q or 4a-q. Diisobutyl 9,10-Dioxo-9,10-dihydroanthracene-2,3-dicarboxylate (3d)
Starting with 1 (316 mg, 1.0 mmol), 3d was isolated as a violet highly viscous oil (338 mg, 83%). ¹H NMR (300 MHz, CDCl3): δ = 0.95 (d, 12 H, J = 6.7 Hz, 4 CH3), 1.96-2.10 (m, 2 H, CH), 4.09 (d, J = 6.7 Hz, 2 CH2O), 7.77-7.81 (m, 2 H, ArH), 8.27-8.30 (m, 2 H, ArH), 8.56 (s, 2 H, ArH). ¹³C NMR (62 MHz, CDCl3): δ = 19.1 (4 CH3), 27.7 (2 CH), 72.4 (2 CH2O), 127.6, 128.0 (2 CH), 133.3, 133.3 (2 C), 134.7 (2 CH), 137.0, 166.2 (2 CO), 181.7 (2 CO). IR (KBr): ν = 3071, 2959, 2929, 2873 (m), 1726, 1679 (s), 1637, 1616 (w)1591, 1521, 1469 (m), 1407, 1391, 1377, 1369, 1333 (w), 1248 (s), 1172, 1134, 1119, 1035, 955, 946, 795, 780 (m), 710 (s), 654, 574 (w) cm-¹. GC-MS (EI, 70 eV): m/z (%) = 408 (100) [M]+, 296 (47), 278 (27), 277 (17), 252 (15), 236 (06), 102 (40). HRMS (ESI+): m/z calcd for C24H24O6 [M]+: 408.15729; found: 408.15730.

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