Journal of Natural Products
Article
71.8 (C-4″), 64.9 (C-6″), 56.6 (OMe-3‴), 43.9 (C-3); HRFABMS
(positive-ion mode) m/z 655.1261 [M + Na]+ (calcd for
C29H28O16Na, 655.1273).
MHz) δ 177.3 (C-4), 168.4 (C-7‴), 165.5 (C-7), 162.5 (C-5), 158.1
(C-8a), 147.0 (C-2), 147.0 (C-3′), 147.0 (C-5′), 146.3 (C-3‴ and C-
5‴), 139.7 (C-4‴), 138.5 (C-4′), 137.6 (C-3), 123.6 (C-1′), 121.2 (C-
1‴), 111.5 (C-6′), 110.2 (C-2′), 110.1 (C-2‴ and C-6‴), 104.6 (C-
4a), 104.2 (C-1″), 99.3 (C-6), 94.4 (C-8), 77.6 (C-3″), 76.0 (C-5″),
74.8 (C-2″), 71.5 (C-4″), 64.4 (C-6″); HRFABMS (positive-ion
mode) m/z 655.0937 [M + Na]+ (calcd for C28H24O17Na, 655.0909).
(2S)-3′-O-β-D-(6″-O-Galloyl)glucopyranosyloxy-5,7,4′-trihydroxy-
(2S)-3′-O-β-D-(2″,6″-di-O-Galloyl)glucopyranosyloxy-5,7,4′,5′-tet-
rahydroxyflavanone (4). Colorless amorphous solid; [α]22 − 30 (c
D
0.9, MeOH); UV (MeOH) λmax (log ε) 206 (4.45), 247 (3.72), 285
(4.12) nm; ECD (c 0.00018 MeOH) ([θ]) 257 (+7800), 288
1
(−11500), 329 (+7800) nm; H NMR (methanol-d4, 400 MHz) δ
flavanone (8). Colorless amorphous solid; [α]22 − 28.2 (c 0.2,
7.13 (2H, s, H-2‴ and H-6‴), 7.09 (2H, s, H-2″″ and H-6″″), 6.64
(1H, d, J = 2.0 Hz, H-6′), 6.61 (1H, d, J = 2.0 Hz, H-2′), 5.87 (1H, d, J
= 2.0 Hz, H-6), 5.85 (1H, d, J = 2.0 Hz, H-8), 5.20 (1H, d, J = 7.0 Hz,
H-1″), 5.20 (overlapping, H-2″), 5.09 (1H, dd, J = 12.0, 3.5 Hz, H-2),
4.63 (1H, dd, J = 12.0, 2.0 Hz, H-6″), 4.48 (1H, dd, J = 12.0, 5.0 Hz,
H-6″), 3.81 (overlapping, H-3″ and H-5″), 3.67 (1H, 9.5, 9.0, H-4″),
2.85 (1H, dd, J = 17.0, 12.0 Hz, H-3ax), 2.59 (1H, dd, J = 17.0, 3.5 Hz,
H-3eq); 13C NMR (methanol-d4, 100 MHz) δ 197.3 (C-4), 168.2 (C-
7), 168.2 (C-7″″), 168.1 (C-7‴), 165.4 (C-5), 164.5 (C-8a), 147.3 (C-
5′), 146.7 (C-3′), 146.5 (C-3‴ and C-5‴), 146.5 (C-3″″ and C-5″″),
140.1 (C-4‴), 139.9 (C-4″″), 137.1 (C-4′), 131.3 (C-1′), 121.3 (C-
1″″), 121.2 (C-1‴), 110.5 (C-2‴ and 6‴), 110.2 (C-6′), 110.2 (C-2″″
and C-6″″), 108.6 (C-2′), 103.3 (C-4a), 102.5 (C-1″), 97.1 (C-6),
96.2 (C-8), 79.9 (C-2), 76.0 (C-3″), 76.0 (C-5″), 75.5 (C-2″), 71.5
(C-4″), 64.3 (C-6″), 43.8 (C-3); HRFABMS (positive-ion mode) m/z
793.1236 [M + Na]+ (calcd for C35H30O20Na, 793.1226).
D
MeOH); UV (MeOH) λmax (log ε) 200 (4.04), 285 (3.71) nm; ECD
(c 0.00021, MeOH) ([θ]) 249 (+4700), 287 (−13500), 328 (+3600)
1
nm; H NMR (DMSO-d6, 400 MHz) δ 12.13 (1H, s, OH-5), 7.17
(1H, d, J = 2.0 Hz, H-2′), 7.01 (1H, dd, J = 8.5, 2.0 Hz, H-6′), 6.95
(2H, s, H-2‴ and H-6‴), 6.85 (1H, d, J = 8.5 Hz, H-5′), 5.89 (1H, d, J
= 2.0 Hz, H-8), 5.87 (1H, d, J = 2.0 Hz, H-6), 5.42 (1H, dd, J = 12.5,
3.0 Hz, H-2), 4.85 (1H, d, J = 7.5 Hz, H-1″), 4.37 (2H, m, H-6″), 3.69
(1H, m, H-5″), 3.45 (overlapping, H-4″), 3.35 (overlapping, H-2″ and
H-3″), 3.22 (1H, dd, J = 17.5, 12.5 Hz, H-3ax), 2.71 (1H, dd, J = 17.5,
3.0 Hz, H-3eq); 13C NMR (DMSO-d6, 100 MHz) δ 196.2 (C-4),
166.6 (C-7), 165.7 (C-7‴), 163.4 (C-8a), 162.7 (C-5), 147.0 (C-4′),
145.5 (C-3‴ and 5‴), 144.9 (C-3′), 139.5 (C-4‴), 129.6 (C-1′), 121.4
(C-6′), 119.3 (C-1‴), 116.0 (C-5′), 114.8 (C-2′), 108.6 (C-2‴ and C-
6‴), 101.8 (C-1″), 101.6 (C-4a), 95.8 (C-6), 95.0 (C-8), 78.1 (C-2),
75.7 (C-3″), 73.7 (C-5″), 73.3 (C-2″), 69.0 (C-4″), 62.7 (C-6″), 41.8
(C-3); HRFABMS (positive-ion mode) m/z 625.1169 [M + Na]+
(calcd for C28H26O15Na, 625.1168).
(2R,3R)-3′-O-β-D-(6″-O-Galloyl)glucopyranosyloxy-5,7,4′,5′-tetra-
hydroxyflavanonol (5). Colorless amorphous solid; [α]22 − 58 (c
D
0.18, MeOH); UV (MeOH) λmax (log ε) 206 (4.38), 249 (3.35), 289
(3.97), 412 (2.95) nm; ECD (c 0.00018, MeOH) ([θ]) 253 (+12000),
292 (−29300), 328 (+10200) nm; 1H NMR (methanol-d4, 400 MHz)
δ 7.04 (2H, s, H-2‴ and H-6‴), 6.84 (1H, d, J = 2.0 Hz, H-2′), 6.75
(1H, d, J = 2.0 Hz, H-6′), 5.92 (1H, d, J = 2.5 Hz, H-6), 5.84 (1H, d, J
= 2.5 Hz, H-8), 4.84 (1H, d, J = 7.0 Hz, H-1″), 4.78 (1H, d, J = 11.5
Hz, H-2), 4.58 (1H, dd, J = 12.5, 2.5 Hz, H-6″), 4.46 (1H, dd, J = 12.5,
5.0 Hz, H-6″), 4.39 (1H, d, J = 11.5 Hz, H-3), 3.72 (1H, m, H-5″),
3.53 (overlapping, H-2″, H-3″, and H-4″); 13C NMR (methanol-d4,
100 MHz) δ 197.9 (C-4), 168.6 (C-7), 168.3 (C-7‴), 165.2 (C-5),
164.2 (C-8a), 147.0 (C-3′), 147.0 (C-5′), 146.4 (C-3‴ and C-5‴),
139.8 (C-4‴), 137.1 (C-4′), 129.4 (C-1′), 121.2 (C-1‴), 111.3 (C-6′),
110.1 (C-2‴ and C-6‴), 109.9 (C-2′), 104.5 (C-1″), 101.7 (C-4a),
97.4 (C-6), 96.2 (C-8), 84.7 (C-2), 77.4 (C-3″), 75.8 (C-5″), 74.9 (C-
4″), 73.6 (C-3), 71.3 (C-2″), 64.4 (C-6″); HRFABMS (positive-ion
mode) m/z 657.1058 [M + Na]+ (calcd for C28H26O17Na, 657.1066).
(2R,3R)-3′-O-β-D-(2″,6″-di-O-Galloyl)glucopyranosyloxy-5,7,4′,5′-
8-O-β-D-[6′-O-(3″-O-Methyl)galloyl]glucopyranosyl-p-tyrosol (9).
1
Colorless amorphous solid; [α]22 − 20 (c 0.4, MeOH); H NMR
D
(methanol-d4, 400 MHz) δ 7.22 (1H, d, J = 2.0 Hz, H-6″), 7.17 (1H,
d, J = 2.0 Hz, H-2″), 6.96 (2H, d, J = 9.0 Hz, H-2 and H-6), 6.65 (2H,
d, J = 9.0 Hz, H-3 and H-5), 4.60 (1H, dd, J = 11.5, 2.5 Hz, H-6′), 4.40
(1H, dd, J = 11.5, 6.5 Hz, H-6′), 4.34 (1H, d, J = 8.0 Hz, H-1′), 3.92
(1H, m, H-8), 3.77 (3H, s, OMe-3″), 3.72 (1H, m, H-8), 3.58 (1H, m,
H-5′), 3.42 (overlapping, H-3′ and H-4′), 3.22 (1H, dd, J = 9.5, 8.0
Hz, H-2′), 2.80 (2H, m, H-7); 13C NMR (methanol-d4, 100 MHz) δ
168.2 (C-7″), 156.7 (C-4), 149.1 (C-3″), 146.3 (C-5″), 140.7 (C-4″),
130.9 (C-2 and C-6), 130.5 (C-1), 121.4 (C-1″), 116.1 (C-3 and C-5),
112.0 (C-6″), 106.1 (C-2″), 104.5 (C-1′), 78.0 (C-3′), 75.5 (C-5′),
75.1 (C-2′), 72.4 (C-8), 72.0 (C-4′), 65.0 (C-6′), 56.6 (OMe-3″), 36.5
(C-7); HRFABMS (positive-ion mode) m/z 489.1385 [M + Na]+
(calcd for C22H26O11Na, 489.1372).
8-O-β-D-(2′,6′-Di-O-galloyl)glucopyranosyl-p-tyrosol (10). Color-
less amorphous solid; [α]22 − 32 (c 1.1, MeOH); 1H NMR
tetrahydroxyflavanonol (6). Colorless amorphous solid; [α]22 − 17
D
D
(methanol-d4, 400 MHz) δ 7.11 (2H, s, H-2″ and H-6″), 7.11 (2H, s,
H-2‴ and 6‴), 6.85 (2H, br d, J = 8.5 Hz, H-2 and H-6), 6.49 (2H, br
d, J = 8.5 Hz, H-3 and H-5), 4.93 (1H, dd, J = 9.5, 8.0 Hz, H-2′), 4.61
(1H, d, J = 8.0 Hz, H-1′), 4.55 (1H, dd, J = 12.0, 2.5 Hz, H-6′), 4.47
(1H, dd, J = 12.0, 5.5 Hz, H-6′), 3.92 (1H, m, H-8), 3.67 (1H, dd, J =
9.5, 9.0 Hz, H-3′), 3.63 (overlapping, H-8), 3.63 (overlapping, H-5′),
3.56 (1H, t, J = 9.0, H-4′), 2.66 (1H, m, H-7); 13C NMR (methanol-
d4, 100 MHz) δ 168.4 (C-7‴), 167.7 (C-7″), 156.6 (C-4), 146.6 (C-3‴
and C-5‴), 146.5 (C-3″ and C-5″), 139.9 (C-4″), 139.9 (C-4‴), 130.9
(C-2 and C-6), 130.8 (C-1), 121.7 (C-1‴), 121.4 (C-1″), 116.1 (C-3
and C-5), 110.5 (C-2‴ and C-6‴), 110.2 (C-2″ and C-6″), 102.5 (C-
1′), 76.2 (C-3′), 75.6 (C-5′), 75.4 (C-2′), 72.1 (C-8), 71.9 (C-4′),
64.6 (C-6′), 36.3 (C-7); HRFABMS (positive-ion mode) m/z
627.1319 [M + Na]+ (calcd for C28H28O15Na, 627.1324).
(c 0.6, MeOH); UV (MeOH) λmax (log ε) 208 (4.43), 249 (3.60), 285
(4.02) nm; ECD (c 0.00018, MeOH) ([θ]) 232 (+18500), 292
1
(−16000), 329 (+9600) nm; H NMR (methanol-d4, 400 MHz) δ
7.13 (2H, s, H-2″″ and H-6″″), 7.09 (2H, s, H-2‴ and H-6‴), 6.71
(2H, s, H-2′ and H-6′), 5.92 (1H, d, J = 1.5 Hz, H-6), 5.84 (1H, d, J =
1.5 Hz, H-8), 5.22 (overlapping, H-1″), 5.21 (overlapping, H-2″), 4.76
(1H, d, J = 11.5 Hz, H-2), 4.60 (1H, br d, J = 12.0, Hz, H-6″), 4.48
(1H, dd, J = 12.0, 5.0 Hz, H-6″), 4.34 (1H, d, J = 11.5 Hz, H-3), 3.80
(overlapping, H-3″ and H-5″), 3.69 (1H, dd, J = 9.5, 9.0 Hz, H-4″);
13C NMR (methanol-d4, 100 MHz) δ 198.0 (C-4), 168.7 (C-7), 168.3
(C-7″″), 168.2 (C-7‴), 165.3 (C-5), 164.3 (C-8a), 147.1 (C-3′), 147.1
(C-5′), 146.6 (C-3″″ and C-5″″), 146.5 (C-3‴ and C-5‴), 140.1 (C-
4″″), 139.9 (C-4‴), 137.6 (C-4′), 129.4 (C-1′), 121.3 (C-1″″), 121.2
(C-1‴), 110.5 (C-2″″ and 6″″), 110.2 (C-6′), 110.2 (C-2‴ and 6‴),
110.0 (C-2′), 102.7 (C-1″), 101.8 (C-4a), 97.5 (C-6), 96.4 (C-8), 84.7
(C-2), 76.0 (C-3″), 76.0 (C-5″), 75.5 (C-2″), 73.7 (C-3), 71.4 (C-4″),
64.3 (C-6″); HRFABMS (positive-ion mode) m/z 809.1153 [M +
Na]+ (calcd for C35H30O21Na, 809.1175).
3′-O-β-D-(6″-O-Galloyl)glucopyranosyloxy-5,7,4′,5′-tetrahydrox-
yflavonol (7). Colorless amorphous solid; [α]22D − 84 (c 0.2, MeOH);
1H NMR (methanol-d4, 400 MHz) δ 7.69 (1H, d, J = 2.0 Hz, H-2′),
7.50 (1H, d, J = 2.0 Hz, H-6′), 7.00 (2H, s, H-2‴ and H-6‴), 6.28
(1H, d, J = 2.0 Hz, H-8), 6.15 (1H, d, J = 2.0 Hz, H-6), 4.85
(overlapping, H-1″), 4.70 (1H, br d, J = 12.5 Hz, H-6″), 4.42 (1H, dd,
J = 12.0, 5.0 Hz, H-6″), 3.75 (1H, m, H-5″), 3.57 (overlapping, H-2″
and H-3″), 3.54 (overlapping, H-4″); 13C NMR (methanol-d4, 100
4-O-β-D-(6′-O-Galloyl)glucopyranosyl-(E)-p-coumaroyl acid (11).
1
Colorless amorphous solid; [α]22 − 90 (c 0.1, MeOH); H NMR
D
(methanol-d4, 400 MHz) δ 7.59 (1H, d, J = 16.0 Hz, H-7), 7.48 (2H,
d, J = 9.0 Hz, H-2 and H-6), 7.12 (2H, s, H-2″ and H-6″), 7.09 (2H, d,
J = 9.0 Hz, H-3 and H-5), 6.35 (1H, d, J = 16.0 Hz, H-8), 4.94 (1H, d,
J = 7.5 Hz, H-1′), 4.64 (1H, dd, J = 12.0, 2.5 Hz, H-6′), 4.34 (1H, dd, J
= 12.0, 7.5 Hz, H-6′), 3.78 (1H, m, H-5′), 3.51 (overlapping, H-2′ and
H-3′), 3.42 (1H, m, H-4′); 13C NMR (methanol-d4, 100 MHz) δ
170.9 (C-9), 168.1 (C-7″), 160.6 (C-4), 146.6 (C-3″ and C-5″), 146.1
(C-7), 140.0 (C-4″), 130.8 (C-2 and C-6), 130.0 (C-1), 121.4 (C-1″),
118.0 (C-5 and C-3), 117.4 (C-8), 110.3 (C-2″ and C-6″), 101.9 (C-
1′), 78.0 (C-3′), 75.8 (C-5′), 74.9 (C-2′), 71.9 (C-4′), 65.0 (C-6′);
F
J. Nat. Prod. XXXX, XXX, XXX−XXX