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DOI: 10.1055/s-0030-1259702
Synthesis of Kaempferol 3-O-[2′′,3′′- and 2′′,4′′-Di-O-(E)-p-coumaroyl]-α-l-rhamnopyranosides
Publikationsverlauf
Publikationsdatum:
08. März 2011 (online)
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
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References and Notes
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.
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.