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

Yan Li; Weizhun Yang; Yuyong Ma; Jiansong Sun; Lei Shan; Wei-Dong Zhang; Biao Yu

doi:10.1055/s-0030-1259702

LETTER

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

Yan Li^a,b, Weizhun Yang^c, Yuyong Ma^a, Jiansong Sun*^a, Lei Shan^c, Wei-Dong Zhang^c, 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

Abstract

All articles of this category

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

Full Text

References

References and Notes

<A NAME="RW32210ST-1A">1a</A> Kaouadji M. Phytochemistry 1990, 29: 2295

<A NAME="RW32210ST-1B">1b</A> Kaouadji M. Morand J.-M. Garcia J. J. Nat. Prod. 1993, 56: 1618

<A NAME="RW32210ST-2">2</A> Mitrokotsa D. Mitaku S. Demetzos C. Harvala C. Mentis A. Perez S. Kokkinopoulos D. Planta Med. 1993, 59: 517

<A NAME="RW32210ST-3">3</A> Ibrahim MA. Mansoor AA. Gross A. Ashfaq MK. Jacob M. Khan SI. Hamann MT. J. Nat. Prod. 2009, 72: 2141

<A NAME="RW32210ST-4A">4a</A> Bloor SJ. Phytochemistry 1995, 38: 1033

<A NAME="RW32210ST-4B">4b</A> Soliman FM. Shehata AH. Khaled AE. Ezzat SM. Molecules 2002, 7: 245

<A NAME="RW32210ST-5A">5a</A> 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

<A NAME="RW32210ST-5B">5b</A> Mahamat A. MacKenzie FM. Brooker K. Monnet DL. Daures JP. Gould IM. Int. J. Antimicrob. Agents 2007, 30: 169

<A NAME="RW32210ST-6">6</A> Garcez WS. Yoshida M. Gottlieb OR. Phytochemistry 1995, 39: 815

<A NAME="RW32210ST-7">7</A> Fiorini C. David B. Fouraste I. Vercauteren J. Phytochemistry 1998, 47: 821

<A NAME="RW32210ST-8">8</A> Rao LJM. Yada H. Ono H. Yoshida M. J. Agric. Food Chem. 2002, 50: 3143

<A NAME="RW32210ST-9">9</A> Kawahara N. Satake M. Goda Y. Chem. Pharm. Bull. 2002, 50: 1619

<A NAME="RW32210ST-10">10</A> 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

<A NAME="RW32210ST-11">11</A> Wang G.-J. Tsai T.-H. Lin L.-C. Phytochemistry 2007, 68: 2455

<A NAME="RW32210ST-12">12</A> Lee S.-S. Lin H.-C. Chen C.-K. Phytochemistry 2008, 69: 2347

<A NAME="RW32210ST-13">13</A> Otsuka N. Liu M.-H. Shiota S. Ogawa W. Kuroda T. Hatano T. Tsuchiya T. Biol. Pharm. Bull. 2008, 31: 1794

<A NAME="RW32210ST-14A">14a</A> Harborne JB. Williams CA. Nat. Prod. Rep. 1995, 12: 639

<A NAME="RW32210ST-14B">14b</A> Harborne JB. Williams CA. Nat. Prod. Rep. 1998, 15: 631

<A NAME="RW32210ST-14C">14c</A> Harborne JB. Williams CA. Nat. Prod. Rep. 2001, 18: 310

<A NAME="RW32210ST-14D">14d</A> Veitch NC. Grayer RJ. Nat. Prod. Rep. 2008, 25: 555

For early reports, see:

<A NAME="RW32210ST-15A">15a</A> Demetzos C. Skaltsounis A.-L. Tillequin F. Koch M. Carbohydr. Res. 1990, 207: 131

<A NAME="RW32210ST-15B">15b</A> Razanamahefa B. Demetzos C. Skaltsounis A.-L. Andriantisiferana M. Tillequin F. Heterocycles 1994, 38: 357

<A NAME="RW32210ST-15C">15c</A> Demetzos C. Skaltsounis A.-L. Razanamahefa B. Tillequin F. J. Nat. Prod. 1994, 57: 1234

<A NAME="RW32210ST-15D">15d</A> Li M. Han X. Yu B. Tetrahedron Lett. 2002, 43: 9467

For early reports, see:

<A NAME="RW32210ST-16A">16a</A> Wagner H. Danninger H. Seligmann O. Nogradi M. Farkas L. Farnsworth N. Chem. Ber. 1970, 103: 3678

<A NAME="RW32210ST-16B">16b</A> 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

<A NAME="RW32210ST-16C">16c</A> Farkas L. Vermes B. Mihály N. Kálmán A. Phytochemistry 1976, 15: 1184

<A NAME="RW32210ST-17">17</A> Yang W. Sun J. Lu W. Li Y. Shan L. Han W. Zhang W.-D. Yu B. J. Org. Chem. 2010, 51: 1504

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.

<A NAME="RW32210ST-19">19</A> Diwu Z. Beachdel C. Klaubert DH. Tetrahedron Lett. 1998, 39: 4987

<A NAME="RW32210ST-20A">20a</A> Li Y. Yang Y. Yu B. Tetrahedron Lett. 2008, 49: 3604

<A NAME="RW32210ST-20B">20b</A> Yang Y. Li Y. Yu B. J. Am. Chem. Soc. 2009, 131: 12076

<A NAME="RW32210ST-20C">20c</A> Li Y. Yang X. Liu Y. Zhu C. Yang Y. Yu B. Chem. Eur. J. 2010, 16: 1871

<A NAME="RW32210ST-20D">20d</A> Yang Y. Li Y. Yu B. Tetrahedron Lett. 2010, 51: 1504

<A NAME="RW32210ST-20E">20e</A> Li Y. Yu B. Chem. Commun. 2010, 46: 6060

<A NAME="RW32210ST-21">21</A> Zhang Z. Mao J. Chen H. Cai M. Tetrahedron Asymmetry 1994, 5: 2283

<A NAME="RW32210ST-22">22</A> Fürstner A. Jeanjean F. Razon P. Wirtz C. Mynott R. Chem. Eur. J. 2003, 9: 307

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.

<A NAME="RW32210ST-24A">24a</A> Maloney DJ. Hecht SM. Org. Lett. 2005, 7: 1097

<A NAME="RW32210ST-24B">24b</A> Smith JA. Maloney DJ. Clark DE. Xu Y. Hecht SM. Lannigan DA. Bioorg. Med. Chem. 2006, 14: 6034

<A NAME="RW32210ST-24C">24c</A> Smith JA. Maloney DJ. Hecht SM. Lannigan DA. Bioorg. Med. Chem. 2007, 15: 5018