Abstract
In the presence of triethylamine, the Diels-Alder reaction of 3-hydroxy-2-pyrones with 1,4-naphthoquinones by a decarboxylation-oxidation process gave anthraquinone derivatives in good to excellent yields.
Key words
3-hydroxy-2-pyrone - tandem reactions - Diels-Alder reactions - anthraquinone - oxidations
References and Notes
1a Huang HC.
Chu SH.
Chao PDL.
Eur. J. Pharmacol.
1991,
198:
211
1b Barnard DL.
Huffman JH.
Morris JL.
Wood SG.
Hughes BG.
Sidwell RW.
Antivir. Res.
1992,
17:
63
1c Kuo YC.
Sun CM.
Ou JC.
Tsai WJ.
Life Sci.
1997,
61:
2335
1d Koyama J.
Morita I.
Tagahara K.
Nobukuni Y.
Mukainaka T.
Kuchida M.
Tokuda H.
Nishino H.
Cancer Lett.
2002,
182:
135
2a Krhon K.
Baltus W.
Tetrahedron
1988,
44:
49
2b Matsumoto T.
Jona H.
Katsuki M.
Suzuki K.
Tetrahedron Lett.
1991,
32:
5103
2c Ueberbacher BJ.
Osprian I.
Mayer SF.
Faber K.
Eur. J. Org. Chem.
2005,
1266
3a Imamura N.
Kakinuma K.
Ikekawa N.
Tanaka H.
Omura S.
J. Antibiot.
1981,
34:
1517
3b Imamura N.
Kakinuma K.
Ikekawa N.
Tanaka H.
Omura S.
J. Antibiot.
1982,
35:
602
3c Danishefsky S.
Uang BJ.
Quallich G.
J. Am. Chem. Soc.
1984,
106:
2453
3d Cambie RC.
Pausler MG.
Rutledge PS.
Woodgate PD.
Tetrahedron Lett.
1985,
26:
5341
3e Matsumoto T.
Katsuki M.
Jona H.
Suzuki K.
Tetrahedron Lett.
1989,
30:
6185
4a Politi M.
Sanogo R.
Ndjoko K.
Guilet D.
Wolfender J.-L.
Hostettmann K.
Morelli I.
Phytochem. Anal.
2004,
15:
355
4b Don M.-J.
Huang Y.-J.
Huang R.-L.
Lin Y.-L.
Chem. Pharm. Bull.
2004,
52:
866
4c Ahmad R.
Shaari K.
Lajis NH.
Hamzah AS.
Ismail NH.
Kitajima M.
Phytochemistry
2005,
66:
1141
5a Huang H.-S.
Chiou J.-F.
Fong Y.
Hou C.-C.
Lu Y.-C.
Wang J.-Y.
Shin J.-W.
Pan Y.-R.
Lin J.-J.
J. Med. Chem.
2003,
46:
3300
5b Teich L.
Daub KS.
Krugel V.
Nissler L.
Gebhardt R.
Eger K.
Bioorg. Med. Chem.
2004,
12:
5961
6 Liebesking LS.
Iyer S.
Jewell CF.
J. Org. Chem.
1986,
51:
3065
7 Khanapure SP.
Reddy RT.
Biehl ER.
J. Org. Chem.
1987,
52:
5685
8a Hauser FM.
Prasanna S.
J. Org. Chem.
1982,
47:
383
8b Hauser FM.
Mal D.
J. Am. Chem. Soc.
1983,
105:
5688
9 Underwood HW.
Walsh WL.
J. Am. Chem. Soc.
1936,
58:
646
10 Sartori G.
Casnati G.
Bigi F.
Robles P.
Tetrahedron Lett.
1987,
28:
1533
11a Komiyama T.
Takaguchi Y.
Tsuboi S.
Tetrahedron Lett.
2004,
45:
6299
11b Komiyama T.
Takaguchi Y.
Gubaidullin AT.
Mamedov VA.
Litvinov IA.
Tsuboi S.
Tetrahedron
2005,
61:
2541
12 Without triethylamine, the reaction of 1a and 2a gave only traces of desired compound 4a .
13 Okamura H.
Iwagawa T.
Nakatani M.
Tetrahedron Lett.
1995,
36:
5939
14
Anthraquinone 4c; Typical Procedure. To a stirred solution of 1,4-naphthoquinone 2a (72 mg, 0.46 mmol) and 2-pyrone 1c (50 mg, 0.23 mmol) in toluene (5 mL) was added Et3 N (2 mg, 0.02 mmol) and the reaction mixture was heated to reflux for 2 h. Then the reaction mixture was allowed to cool to r.t. After evaporation of the solvent, the crude product was purified by column chromatography (hexane-EtOAc, 50:1) to give anthraquinone 4c (70 mg, 93%) as an orange solid; mp 210-212 °C. IR (neat): 1662, 1630, 1591, 1424, 1349, 1285, 1217, 1126, 1017, 747, 708 cm-1 . 1 H NMR (300 MHz, CDCl3 ): δ = 7.07 (d, J = 8.1 Hz, 1 H), 7.47-7.49 (m, 3 H), 7.57-7.61 (m, 2 H), 7.67 (d, J = 8.1 Hz, 1 H), 7.80-7.85 (m, 2 H), 8.27-8.34 (m, 2 H), 13.3 (br, 1 H). Anal. Calcd for C20 H12 O3 S: C, 72.27; H, 3.64. Found: C, 72.48; H, 3.66.
