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Synlett 2011(7): 915-918  
DOI: 10.1055/s-0030-1259702
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Kaempferol 3-O-[2′′,3′′- and 2′′,4′′-Di-O-(E)-p-coumaroyl]-α-l-rhamnopyranosides

Yan Lia,b, Weizhun Yangc, Yuyong Maa, Jiansong Sun*a, Lei Shanc, Wei-Dong Zhangc, Biao Yu*a
a State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: byu@mail.sioc.ac.cn;
b Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. of China
c Department of Phytochemistry, School of Pharmacy, Second Military Medical University, Shanghai 200433, P. R. of China
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Publication History

Received 15 September 2010
Publication Date:
08 March 2011 (online)

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Abstract

Kaempferol 3-O-[2′′,3′′- and 2′′,4′′-di-O-(E)-p-coumaroyl]-α-l-rhamnopyranoside, two acylated flavonol 3-O-glycosides with potent inhibitory activity against methicillin-resistant Staphylococcus aureus, were synthesized for the first time, employing glycosyl o-cyclopropylethynylbenzoates as donors and Ph3PAuNTf2 as a catalyst for the construction of the flavonol glycosidic linkages.

Key words

flavonol glycosides - glycosylation - glycosyl o-alkynylbenzoate - antibacterial activity

    References and Notes

  • 1a Kaouadji M. Phytochemistry  1990,  29:  2295 
    Google Scholar
  • 1b Kaouadji M. Morand J.-M. Garcia J. J. Nat. Prod.  1993,  56:  1618 
    Google Scholar
  • 2 Mitrokotsa D. Mitaku S. Demetzos C. Harvala C. Mentis A. Perez S. Kokkinopoulos D. Planta Med.  1993,  59:  517 
    Article in Thieme ConnectGoogle Scholar
  • 3 Ibrahim MA. Mansoor AA. Gross A. Ashfaq MK. Jacob M. Khan SI. Hamann MT. J. Nat. Prod.  2009,  72:  2141 
    CrossrefGoogle Scholar
  • 4a Bloor SJ. Phytochemistry  1995,  38:  1033 
    Google Scholar
  • 4b Soliman FM. Shehata AH. Khaled AE. Ezzat SM. Molecules  2002,  7:  245 
    Google Scholar
  • 5a Diekema DJ. Boots Miller BJ. Vaughn TE. Woolson RF. Yankey JW. Ernst EJ. Flach SD. Ward MM. Franciscus CL. Pfaller MA. Doebbeling BN. Clin. Infect. Dis.  2004,  38:  78 
    Google Scholar
  • 5b Mahamat A. MacKenzie FM. Brooker K. Monnet DL. Daures JP. Gould IM. Int. J. Antimicrob. Agents  2007,  30:  169 
    Google Scholar
  • 6 Garcez WS. Yoshida M. Gottlieb OR. Phytochemistry  1995,  39:  815 
    CrossrefGoogle Scholar
  • 7 Fiorini C. David B. Fouraste I. Vercauteren J. Phytochemistry  1998,  47:  821 
    CrossrefGoogle Scholar
  • 8 Rao LJM. Yada H. Ono H. Yoshida M. J. Agric. Food Chem.  2002,  50:  3143 
    CrossrefGoogle Scholar
  • 9 Kawahara N. Satake M. Goda Y. Chem. Pharm. Bull.  2002,  50:  1619 
    CrossrefGoogle Scholar
  • 10 Kuo Y.-C. Lu C.-K. Huang L.-W. Kuo Y.-H. Chang C. Hsu F.-L. Lee T.-H. Planta Med.  2005,  71:  412 
    Article in Thieme ConnectGoogle Scholar
  • 11 Wang G.-J. Tsai T.-H. Lin L.-C. Phytochemistry  2007,  68:  2455 
    CrossrefGoogle Scholar
  • 12 Lee S.-S. Lin H.-C. Chen C.-K. Phytochemistry  2008,  69:  2347 
    CrossrefGoogle Scholar
  • 13 Otsuka N. Liu M.-H. Shiota S. Ogawa W. Kuroda T. Hatano T. Tsuchiya T. Biol. Pharm. Bull.  2008,  31:  1794 
    CrossrefGoogle Scholar
  • 14a Harborne JB. Williams CA. Nat. Prod. Rep.  1995,  12:  639 
    Google Scholar
  • 14b Harborne JB. Williams CA. Nat. Prod. Rep.  1998,  15:  631 
    Google Scholar
  • 14c Harborne JB. Williams CA. Nat. Prod. Rep.  2001,  18:  310 
    Google Scholar
  • 14d Veitch NC. Grayer RJ. Nat. Prod. Rep.  2008,  25:  555 
    Google Scholar
  • For early reports, see:
  • 15a Demetzos C. Skaltsounis A.-L. Tillequin F. Koch M. Carbohydr. Res.  1990,  207:  131 
    Google Scholar
  • 15b Razanamahefa B. Demetzos C. Skaltsounis A.-L. Andriantisiferana M. Tillequin F. Heterocycles  1994,  38:  357 
    Google Scholar
  • 15c Demetzos C. Skaltsounis A.-L. Razanamahefa B. Tillequin F. J. Nat. Prod.  1994,  57:  1234 
    Google Scholar
  • 15d Li M. Han X. Yu B. Tetrahedron Lett.  2002,  43:  9467 
    Google Scholar
  • For early reports, see:
  • 16a Wagner H. Danninger H. Seligmann O. Nogradi M. Farkas L. Farnsworth N. Chem. Ber.  1970,  103:  3678 
    Google Scholar
  • 16b Vermes B. Farkas L. Nógrádi M. In Topics in Flavonoid Chemistry and Biochemistry   Farkas L. Gábor M. Kállay F. Elsevier; Amsterdam: 1975.  p.162-170  
    Google Scholar
  • 16c Farkas L. Vermes B. Mihály N. Kálmán A. Phytochemistry  1976,  15:  1184 
    Google Scholar
  • 17 Yang W. Sun J. Lu W. Li Y. Shan L. Han W. Zhang W.-D. Yu B. J. Org. Chem.  2010,  51:  1504 
    Google Scholar
  • 19 Diwu Z. Beachdel C. Klaubert DH. Tetrahedron Lett.  1998,  39:  4987 
    CrossrefGoogle Scholar
  • 20a Li Y. Yang Y. Yu B. Tetrahedron Lett.  2008,  49:  3604 
    Google Scholar
  • 20b Yang Y. Li Y. Yu B. J. Am. Chem. Soc.  2009,  131:  12076 
    Google Scholar
  • 20c Li Y. Yang X. Liu Y. Zhu C. Yang Y. Yu B. Chem. Eur. J.  2010,  16:  1871 
    Google Scholar
  • 20d Yang Y. Li Y. Yu B. Tetrahedron Lett.  2010,  51:  1504 
    Google Scholar
  • 20e Li Y. Yu B. Chem. Commun.  2010,  46:  6060 
    Google Scholar
  • 21 Zhang Z. Mao J. Chen H. Cai M. Tetrahedron Asymmetry  1994,  5:  2283 
    CrossrefGoogle Scholar
  • 22 Fürstner A. Jeanjean F. Razon P. Wirtz C. Mynott R. Chem. Eur. J.  2003,  9:  307 
    CrossrefGoogle Scholar
  • 24a Maloney DJ. Hecht SM. Org. Lett.  2005,  7:  1097 
    Google Scholar
  • 24b Smith JA. Maloney DJ. Clark DE. Xu Y. Hecht SM. Lannigan DA. Bioorg. Med. Chem.  2006,  14:  6034 
    Google Scholar
  • 24c Smith JA. Maloney DJ. Hecht SM. Lannigan DA. Bioorg. Med. Chem.  2007,  15:  5018 
    Google Scholar
18

3,7-Di- O -benzyl-kaempferol
¹H NMR (300 MHz, CDCl3): δ = 12.72 (s, 1 H), 10.29 (s, 1 H), 7.93 (d, J = 8.8 Hz, 2 H), 7.47-7.32 (m, 9 H), 6.92 (d, J = 8.8 Hz, 2 H), 6.74 (d, J = 2.0 Hz, 1 H), 6.42 (d, J = 2.0 Hz, 1 H), 5.19 (s, 2 H), 5.03 (s, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 178.0, 164.0, 161.0, 160.2, 156.5, 156.1, 136.6, 136.4, 136.0, 130.3, 128.4, 128.3, 128.2, 128.0, 127.7, 120.5, 115.4, 105.2, 98.3, 93.0, 73.3, 69.9, 40.1, 39.9, 39.7, 39.5, 39.3, 39.1, 38.9.

23

Spectroscopic Data for Synthetic Compounds
Compound 1: [α]D ²5 72.1 (c 0.2, MeOH); lit.4 [α] 89.6. ¹H NMR (400 MHz, CD3OD): δ = 7.87 (d, J = 8.8 Hz, 2 H), 7.62 (d, J = 15.8 Hz, 1 H), 7.60 (d, J = 15.8 Hz, 1 H), 7.46 (d, J = 8.6 Hz, 1 H), 7.38 (d, J = 8.5 Hz, 1 H), 6.99 (d, J = 8.7 Hz, 1 H), 6.81 (d, J = 8.6 Hz, 1 H), 6.75 (d, J = 8.5 Hz, 1 H), 6.41 (d, J = 2.0 Hz, 1 H), 6.38 (d, J = 15.8 Hz, 1 H), 6.29 (d, J = 15.8 Hz, 1 H), 6.21 (d, J = 2.0 Hz, 1 H), 5.82 (dd, J = 1.5, 3.2 Hz, 1 H), 5.60 (s, 1 H), 5.28 (dd, J = 3.2, 9.5 Hz, 1 H), 3.64 (t, J = 9.8 Hz, 1 H), 3.51-3.58 (m, 1 H), 1.05 (d, J = 6.0 Hz, 3 H). ¹³C NMR (100 MHz, CD3OD): δ = 179.4, 168.5, 167.8, 165.9, 163.4, 161.8, 161.5, 161.3, 159.1, 158.6, 147.8, 147.0, 135.5, 131.9, 131.4, 131.2, 127.1 (d), 122.4, 116.9, 116.8 (d), 114.9, 114.4, 105.9, 100.3, 99.9, 94.8, 73.0, 72.2, 71.0, 70.9, 17.8. ESI-HRMS: m/z calcd for C39H31O14 [M - H]-: 723.1719; found: 723.1740.
Compound 2: [α]D ²5 -36.6 (c 0.3, MeOH); lit.¹0 [α] -44.8. ¹H NMR (500 MHz, CD3OD): δ = 7.81 (d, J = 8.7 Hz, 2 H), 7.69 (d, J = 15.6 Hz, 1 H), 7.58 (d, J = 15.6 Hz, 1 H), 7.53 (d, J = 8.7 Hz, 2 H), 7.50 (d, J = 8.7 Hz, 2 H), 7.04 (d, J = 8.7 Hz, 2 H), 6.84 (d, J = 8.7 Hz, 2 H), 6.81 (d, J = 8.7 Hz, 2 H), 6.43 (d, J = 16.1 Hz, 1 H), 6.40 (d, J = 1.4 Hz, 1 H), 6.32 (d, J = 15.6 Hz, 1 H), 6.20 (d, J = 1.8 Hz, 1 H), 5.76 (s, 1 H), 5.43 (t, J = 1.4 Hz, 1 H), 4.98 (t, J = 9.9 Hz, 1 H), 4.55 (s, 1 H), 4.16 (dd, J = 3.2, 9.7 Hz, 1 H), 3.29-3.26 (m, 1 H), 0.86 (d, J = 6.0 Hz, 3 H). ¹³C NMR (125 MHz, CD3OD): δ = 179.3, 168.5, 168.4, 166.0, 163.3, 161.9, 161.4, 159.5, 158.6, 147.5, 147.0, 134.7, 132.0, 131.4, 131.3, 127.2, 122.5, 116.8, 116.7, 115.0, 114.7, 106.0, 100.0, 99.2, 94.9, 74.7, 73.2, 69.8, 68.5, 17.7.