Initial Synthesis of Valoneic and Woodfordinic Acid Dilactones

Abstract

The naturally occurring polyphenolic compounds, valoneic and woodfordinic acid dilactones, were synthesized through the classical Ullmann coupling reaction as the key step. To prepare the diaryl ether component, the Ullmann condensation method was applied using the corresponding phenol and arylbromide.

Key words

polyphenol - Ullmann reaction - biaryl - diaryl ether - lactone

• References and Notes

• 1 For a review on polyphenolic compounds, see: Quideau S, Deffieux D, Douat-Casassus C, Pouységu L. Angew. Chem. Int. Ed. 2011; 50: 586
• 2a Vattem DA, Shetty K. J. Food. Biochem. 2005; 29: 234
• 2b Ochir S, Nishizawa M, Park BJ, Ishii K, Kanazawa T, Funaki M, Yamagishi T. J. Nat. Med. 2010; 64: 275
• 2c Hosoyama H, Sugimoto A, Suzuki Y, Sakane I, Kakuda T. Yakugaku Zasshi 2003; 123: 599
• 3a Atta-Ur-Rahman; Ngounou FN, Choudhary MI, Malik S, Makhmoor T, Nur-E-Alam M, Zareen S, Lontsi D, Ayafor JF, Sondengam BL. Planta Med. 2001; 67: 335
• 3b Bagchi D, Hassoun EA, Bagchi M, Stohs S. J. Free Radicals Biol. Med. 1993; 15: 217
• 4a Narayanan BA, Geoffroy O, Willingham MC, Re GG, Nixon DW. Cancer Lett. 1999; 136: 215
• 4b Seeram NP, Adams LS, Henning SM, Niu Y, Zhang Y, Nair MG, Heber D. J. Nutr. Biochem. 2005; 16: 360
• 4c Choi YH, Pezzuto JM, Kinghorn AD, Farnsworth NR. Planta Med. 1988; 54: 511
• 4d Constantinou A, Stoner GD, Mehta R, Rao K, Runyan C, Moon R. Nutr. Cancer 1995; 23: 121
• 5 Cheng X.-F, Meng Z.-M, Chen Z.-L. Phytochemistry 1998; 49: 2193
• 6a Sasov SA, Petrova MF, Yartseva IV. Khim. Prir. Soedin. 1986; 106
• 6b Sasov SA, Tolkachev VN, Yartseva IV, Tolkachev ON. Vopr. Biol. Med. Farm. Khim. 2010; 24
• 7a Wyrepkowski CC, da Costa DL. M. G, Sinhorin AP, Vilegas W, De Grandis RA, Resende FA, Varanda EA, dos Santos LC. Molecules 2014; 19: 16039
• 7b Unno T, Sugimoto A, Kakuda T. J. Ethnopharm. 2004; 93: 391
• 7c Marzouk MS. A. Phytochem. Anal. 2008; 19: 541
• 7d Gođevac D, Tešević V, Vajs V, Milosavljević S, Stanković M. Food Chem. Toxicol. 2009; 47: 2853
• 7e de la Rosa LA, Alvarez-Parrilla E, Shahidi F. J. Agric. Food Chem. 2011; 59: 152
• 7f Mämmelä P, Savolainen H, Lindroos L, Kangas J, Vartiainen T. J. Chromatogr. A 2000; 891: 75
• 7g Hirano Y, Kondo R, Sakai K. J. Wood Sci. 2003; 49: 339
• 7h Fernandes A, Fernandes I, Cruz L, Mateus N, Cabral M, de Freitas V. J. Agric. Food Chem. 2009; 57: 11154
• 7i Fernandes A, Sousa A, Mateus N, Cabral M, de Freitas V. Food Chem. 2011; 125: 1398
• 7j Fischer UA, Carle R, Kammerer DR. Food Chem. 2011; 127: 807
• 7k Kiss AK, Granica S, Stolarczyk M, Melzig MF. Food Chem. 2012; 131: 1015
• 7l Garcia R, Soares B, Dias CB, Freitas AM. C, Cabrita M. J. Eur. Food Res. Technol. 2012; 235: 457
• 7m Cantos E, Espín JC, López-Bote C, de la Hoz L, Ordóñez JA, Tomás-Barberán FA. J. Agric. Food Chem. 2003; 51: 6248
• 7n Yoshida T, Tanei S, Liu Y.-Z, Yuan K, Ji C.-R, Okuda T. Phytochemistry 1993; 32: 1287
• 7o Barakat HH, Hussein SA. M, Marzouk MS, Merfort I, Linscheid M, Nawwar MA. M. Phytochemistry 1997; 46: 935
• 7p Boulekbache-Makhlouf L, Meudec E, Chibane M, Mazauric J.-P, Slimani S, Henry M, Cheynier V, Madani K. J. Agric. Food Chem. 2010; 58: 12615
• 7q Wu S.-B, Dastmalchi K, Long C, Kennelly EJ. J. Agric. Food Chem. 2012; 60: 7513
• 7r Boulekbache-Makhlouf L, Meudec E, Mazauric J.-P, Madani K, Cheynier V. Phytochem. Anal. 2013; 24: 162
• 7s Omar R, Li L, Yuan T, Seeram NP. J. Nat. Prod. 2012; 75: 1505
• 7t Yoshida T, Jin Z.-X, Okuda T. Phytochemistry 1991; 30: 2747
• 7u Yoshida T, Nakazawa T, Hatano T, Yang R.-C, Yang L.-L, Yen K.-Y, Okuda T. Phytochemistry 1994; 37: 241
• 7v Scumidt OT, Komarek E. Justus Liebigs Ann. Chem. 1955; 156
• 8a Okuda T, Yoshida T, Hatano T, Ito H. Chemistry and Biology of Ellagitannins. An Underestimated Class of Bioactive Plant Polyphenols . Quideau S. World Scientific Publishing; Singapore: 2009. Chap. 1
• 8b Khanbabaee K, van Ree T. Nat. Prod. Rep. 2001; 18: 641
• 8c Yoshida T, Amakura Y, Yoshimura M. Int. J. Mol. Sci. 2010; 11: 79
• 9 For an example, see: Alam A, Tsuboi S. Tetrahedron 2007; 63: 10454

For reviews, see:
• 10a Alberico D, Scott ME, Lautens M. Chem. Rev. 2007; 107: 174
• 10b Hassan J, Sévignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
• 11 Ley SV, Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400 ; and references cited therein

We already reported several syntheses of the related compounds, see:
• 12a Abe H, Sahara Y, Matsuzaki Y, Takeuchi Y, Harayama T. Tetrahedron Lett. 2008; 49: 605
• 12b Shioe K, Sahara Y, Horino Y, Harayama T, Takeuchi Y, Abe H. Tetrahedron 2011; 67: 1960
• 12c Shioe K, Ishikura S, Horino Y, Abe H. Chem. Pharm. Bull. 2013; 61: 1308
• 13 Ohzeki T, Mori K. Biosci. Biotechnol. Biochem. 2003; 67: 2584
• 14 Alam A, Takaguchi Y, Ito H, Yoshida T, Tsuboi S. Tetrahedron 2005; 61: 1909
• 15 Woodfordinic Acid Dilactone (2)Under H₂ atmosphere, a mixture of 11 (150 mg, 95 μmol), MeOH (5 mL), EtOAc (5 mL), and Pd/C (10 wt%, 15 mg) was stirred for 15 h at r.t. After filtration with Celite, the filtrate was evaporated. Gray solid of 2 (60.7 mg, 100%) was obtained; mp >300 °C [lit.^6a decomp. 300 °C]. IR (KBr): 3320, 1719, 1617, 1351, 1049 cm^–1. ¹H NMR (500 MHz, MeOH-d ₄): δ = 7.13 (2 H, s, ArH), 7.18 (2 H, s, ArH). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 106.5, 108.2, 109.0, 113.5, 114.7, 135.2, 136.4, 138.9, 139.4, 141.4, 142.8, 149.8, 165.9.
• 16 Tian H, Vogel R, Amici L, Tamagnan G, Baldwin RM. J. Labelled Compd. Radiopharm. 2006; 49: 1247
• 17 Su X, Surry DS, Spandl RJ, Spring DR. Org. Lett. 2008; 10: 2593
• 18 Valoneic Acid Dilactone (3)Valoneic acid dilactone (3) was obtained by the method similar to the protocol for 2 in 80% yield, mp >300 °C. IR (KBr): 3019 (br), 1710, 1610, 1340, 1187, 1107, 1044 cm^–1. ¹H NMR (500 MHz, MeOH-d ₄): δ = 6.75 (1 H, s, ArH), 7.09 (1 H, s, ArH), 7.11 (1 H, s, ArH). ¹³C NMR (125 MHz, MeOH-d ₄): δ = 108.8, 110.3, 111.0, 115.5, 119.7, 121.6, 122.6, 123.0, 138.1, 138.4, 139.1, 140.7, 140.9, 143.6, 144.5, 144.9, 145.3, 147.1, 168.9, 171.0, 171.2.