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B. Hao et al. / Phytochemistry xxx (2016) xxx–xxx
3c 19%; 1H NMR (500 MHz, (CD3)2CO, 221 K) 12.18 (1H, s,
J = 7.0 Hz, CH3); 13C NMR (125 MHz, (CD3)2CO, 293 K) 195.4,
166.4, 163.9, 160.7, 159.3, 134.8, 126.8 (2C), 113..9 (2C), 102.1,
101.9, 96.0, 95.9, 63.2, 48.7, 14.2.
5-OH), 10.24 (1H, s, 7-OH), 8.68 (2H, s, 30,50-0H), 8.20 (1H, s,
40-OH), 6.77 (1H, s, 2-OH), 6.73 (2H, s, 20,60-H), 5.98 (1H, m, 6-H),
5.97 (1H, s, 8-H), 3.22 (1H, dd, J = 2.7, 17.0 Hz, H-3a), 2.75 (1H, d,
J = 16.9 Hz, 3-Hb); 13C NMR (125 MHz, (CD3)2CO, 221 K) 195.9,
166.3, 163.8, 160.7, 145.2 (2C), 133.6, 133.0, 104.5 (2C), 102.2,
101.9, 96.0, 95.7, 48.9.
3l 75%; 1H NMR (500 MHz, (CD3)2CO, 222 K) 12.18 (1H, s, 5-OH),
10.29 (1H, s, 7-OH), 7.64 (2H, d, J = 8.6 Hz, 20,60-H), 7.01 (2H, d,
J = 8.6 Hz, 30,50-H), 7.00 (1H, s, 2-OH), 6.01 (1H, s, 6-H), 5.99 (1H, d,
J = 1.7 Hz, 8-H), 4.08 (2H, t, J = 6.0 Hz, CH2OAr), 3.74 (2H, q,
J = 5.5 Hz, CH2OH), 3.26 (1H, dd, J = 2.6, 16.9 Hz, H-3a), 2.83 (1H, d,
J = 16.9 Hz, 3-Hb), 1.96 (2H, qu, J = 6.0 Hz, CH2); 13C NMR
(125 MHz, (CD3)2CO, 220 K) 195.8, 166.4, 163.8, 160.6, 159.3,
134.6, 127.0 (2C), 113.7 (2C), 102.2, 101.9, 96.0, 95.8, 64.1, 57.7,
48.8, 32.1.
3d 49%; 1H NMR (500 MHz, (CD3)2CO, 220 K) 12.20 (1H, s,
5-OH), 10.28 (1H, s, 7-OH), 8.54 (2H, s, 40-0H), 7.31 (1H, d,
J = 2.0 Hz, 20-H), 7.18 (1H, dd, J = 2.0, 8.0 Hz, 60H), 6.94 (1H, s,
2-OH), 6.89 (1H, d, J = 8.0 Hz, 50-H), 2-OH), 5.99–5.98 (2H, m,
6,8-H), 3.86 (3H, s, OMe), 3.31 (1H, dd, J = 2.8, 16.9 Hz, H-3a),
2.82 (1H, d, J = 16.9 Hz, 3-Hb); 13C NMR (125 MHz, (CD3)2CO,
220 K) 195.9, 166.4, 163.8, 160.7, 146.9, 146.7, 134.0, 117.9,
114.3, 108.7, 102.3, 101.9, 96.0, 95.7, 55.0, 48.9.
3m 44%; 1H NMR (500 MHz, (CD3)2CO, 298 K) 12.07 (1H, s, 5-
OH), 9.60 (1H, s, 7-OH), 7.63 (2H, d, J = 8.8 Hz, 20,60-H), 6.99 (2H, d,
J = 8.6 Hz, 30,50-H), 6.44 (1H, s, 2-OH), 6.02–5.99 (2H, m, 6,8-H),
4.05 (2H, t, J = 6.4 Hz, CH2OAr), 3.56 (2H, t, J = 6.5 Hz, CH2OH), 3.21
(1H, d, J = 16.9 Hz, H-3a), 2.89 (1H, d, J = 16.9 Hz, 3-Hb), 1.80 (2H,
m, CH2), 1.58–1.55 (6H, m, 3CH2); 13C NMR (125 MHz, (CD3)2CO,
298 K) 195.3, 166.4, 163.9, 160.7, 159.5, 134.7, 126.8 (2C), 114.0
(2C), 102.1, 102.0, 96.0, 95.9, 67.7, 61.5, 48.8, 32.8, 28.5, 25.8, 25.6.
3n 50%; 1H NMR (500 MHz, (CD3)2CO, 294 K) 12.07 (1H, s, 5-OH),
9.60 (1H, s, 7-OH), 7.75 (2H, d, J = 8.7 Hz, 20,60-H), 7.43 (2H, t,
J = 8.2 Hz, Ph), 7.19 (1H, t, J = 7.4 Hz, Ph), 7.07 (4H, d, J = 8.7 Hz,
30,50-H, Ph), 6.55 (1H, s, 2-OH), 6.04 (1H, d, J = 2.0 Hz, 6-H), 6.01
(1H, d, J = 2.0 Hz, 8-H), 3.26 (1H, d, J = 16.9 Hz, H-3a), 2.93 (1H, d,
J = 16.8 Hz, 3-Hb); 13C NMR (125 MHz, (CD3)2CO, 293 K) 195.1,
166.4, 164.0, 160.5, 157.8, 156.9, 137.6, 130.0 (2C), 127.3 (2C),
123.8, 119.1 (2C), 118.0 (2C), 102.1, 101.8, 96.0, 96.0, 48.7.
3o 90%; 1H NMR (500 MHz, (CD3)2CO, 292 K) 12.07 (1H, s, 5-OH),
9.60 (1H, s, 7-OH), 7.61 (2H, d, J = 8.2 Hz, 20,60-H), 7.27 (2H, d,
J = 8.0 Hz, 30,50-H), 6.48 (1H, s, 2-OH), 6.03 (1H, d, J = 1.9 Hz, 6-H),
5.99 (1H, d, J = 2.0 Hz, 8-H), 3.22 (1H, d, J = 16.9 Hz, H-3a), 2.90
(1H, d, J = 16.9 Hz, 3-Hb), 2.37 (3H, s, Me); 13C NMR (125 MHz,
(CD3)2CO, 292 K) 195.2, 166.3, 163.9, 160.7, 139.9, 138.3, 128.8
(2C), 125.4 (2C), 102.1, 102.0, 96.0, 95.9, 48.7, 20.2.
3e 33%; 1H NMR (500 MHz, (CD3)2CO, 220 K) 12.20 (1H, s,
5-OH), 10.41 (1H, s, 7-OH), 8.17 (1H, s, 40-0H), 7.01 (2H, s, 20,60-
H), 6.96 (1H, s, 2-OH), 6.00–5.98 (2H, m, 6,8-H), 3.84 (6H, s, 30,50-
OMe), 3.33 (1H, d, J = 17.0 Hz, H-3a), 2.81 (1H, d, J = 17.0 Hz,
3-Hb); 13C NMR (125 MHz, (CD3)2CO, 220 K) 195.8, 166.5, 163.8,
160.7, 147.1 (2C), 135.3, 132.9, 102.4, 102.1 (2C), 101.8, 96.1,
95.8, 55.3 (2C), 48.8.
3f 52%; 1H NMR (500 MHz, (CD3)2CO, 222 K) 12.18 (1H, s, 5-OH),
10.21 (1H, s, 7-OH), 7.66 (2H, d, J = 8.7 Hz, 20,60-H), 7.02 (1H, d,
J = 8.8 Hz, 30,50-H), 6.94 (1H, s, 2-OH), 6.00 (1H, d, J = 1.8 Hz, 6-H),
5.98 (1H, d, J = 1.8 Hz, 8-H), 3.83 (3H, s, 40-OMe), 3.29 (1H, d,
J = 16.9 Hz, H-3a), 2.83 (1H, d, J = 17.0 Hz, 3-Hb); 13C NMR
(125 MHz, (CD3)2CO, 220 K) 195.8, 166.4, 163.8, 160.6, 159.8,
134.7, 127.0 (2C), 113.3 (2C), 102.2, 101.9, 96.0, 95.7, 54.8, 48.7.
3g 65%; 1H NMR (500 MHz, (CD3)2CO, 292 K) 12.08 (1H, s,
5-OH), 9.70 (1H, s, 7-OH), 7.75 (2H, d, J = 7.0 Hz 20,60-H), 7.47
(2H, t, J = 7.2 Hz, 30,50-H), 7.42 (1H, t, J = 7.0 Hz, 40-H), 6.56 (1H, s,
2-OH), 6.05 (1H, br s, 60-H), 6.01 (1H, d, J = 1.6 Hz, 8-H), 3.24 (1H,
d, J = 16.8 Hz, H-3a), 2.92 (1H, d, J = 16.9 Hz, 3-Hb); 13C NMR
(125 MHz, (CD3)2CO, 293 K) 195.1, 166.4, 164.0, 160.6, 142.7,
128.7, 128.5 (2C), 125.4 (2C), 102.1, 101.9, 96.1, 96.0, 48.6.
3h 76%; 1H NMR (500 MHz, (CD3)2CO, 220 K) 12.16 (1H, s,
5-OH), 10.41 (1H, s, 7-OH), 7.24 (1H, s, 20-H), 7.23 (1H, d,
J = 7.9 Hz, 50-H), 6.96 (1H, dd, J = 1.5, 7.6 Hz, 60-H), 6.11 (2H, s,
OCH2O), 6.00–5.98 (2H, m, 6,8-H), 5.76 (1H, d, J = 3.1 Hz, 2-OH),
3.27 (1H, dd, J = 3.3, 17.2 Hz, H-3a), 2.83 (1H, d, J = 16.8 Hz, 3-
Hb); 13C NMR (125 MHz, (CD3)2CO, 220 K) 195.7, 166.5, 163.8,
160.5, 147.9, 147.6, 136.8, 119.1, 107.7, 106.4, 102.1, 101.8,
101.7, 96.0, 95.8, 48.6.
3p 73%; 1H NMR (500 MHz, (CD3)2CO, 293 K) 12.08 (1H, s,
5-OH), 9.65 (1H, s, 7-OH), 7.64 (2H, d, J = 8.1 Hz, 20,60-H), 7.30
(2H, d, J = 8.1 Hz, 30,50-H), 6.48 (1H, s, 2-OH), 6.04 (1H, d,
J = 1.9 Hz, 6-H), 6.01 (1H, d, J = 2.0 Hz, 8-H), 3.23 (1H, d,
J = 16.9 Hz, H-3a), 2.91 (1H, d, J = 16.9 Hz, 3-Hb), 2.69 (2H, q,
J = 7.6 Hz, ArCH2), 1.24 (3H, t, J = 7.6 Hz, Me); 13C NMR (125 MHz,
(CD3)2CO, 293 K) 195.2, 166.4, 163.9, 160.7, 144.8, 140.1, 127.7
(2C), 125.5 (2C), 102.1, 102.0, 96.0, 96.0, 48.7, 28.2, 15.2.
3q 51%; 1H NMR (500 MHz, (CD3)2CO, 220 K) 12.18 (1H, s,
5-OH), 10.31 (1H, s, 7-OH), 7.66 (2H, d, J = 8.3 Hz, 20,60-H), 7.53
(2H, d, J = 8.3 Hz, 30,50-H), 6.96 (1H, s, 2-OH), 6.00 (1H, s, 6-H),
5.99 (1H, d, J = 2.0 Hz, 8-H), 3.31 (1H, dd, J = 2.6, 16.9 Hz, H-3a),
2.85 (1H, d, J = 17.0 Hz, 3-Hb), 1.32 (9H, s, (CH3)3); 13C NMR
(125 MHz, (CD3)2CO, 221 K) 195.7, 166.4, 163.8, 160.6, 151.4,
139.8, 125.4 (2C), 125.3 (2C), 102.2, 101.9, 96.0, 95.8, 48.5, 34.4,
30.7 (3C).
3i 70%; 1H NMR (500 MHz, (CD3)2CO, 221 K) 12.16 (1H, s, 5-OH),
10.30 (1H, s, 7-OH), 9.05 (2H, s, 30,50-0H), 6.88 (1H, s, 2-OH), 6.68
(2H, d, J = 2.5 Hz, 20,60-H), 6.37 (1H, t, J = 2.1 Hz, 40-H), 6.00 (1H, d,
J = 2.1 Hz, 6-H), 5.98 (1H, d, J = 2.1 Hz, 8-H), 3.24 (1H, dd, J = 2.6,
16.9 Hz, H-3a), 2.79 (1H, d, J = 16.9 Hz, 3-Hb); 13C NMR
(125 MHz, (CD3)2CO, 221 K) 195.6, 166.4, 163.8, 160.5, 158.5
(2C), 145.1, 104.0 (2C), 102.4, 102.0, 101.8, 96.0, 95.8, 48.5.
3j 35%; 1H NMR (500 MHz, (CD3)2CO, 292 K) 12.06 (1H, s, 5-OH),
9.75 (1H, s, 7-OH), 8.62 (1H, s, 40-0H), 7.28 (1H, t, J = 7.9 Hz, 50-H),
7.21–7.17 (2H, m, 20,60-H), 6.88 (1H, dd, J = 2.4, 8.0 Hz, 40-H), 6.51
(1H, d, J = 1.9 Hz, 2-OH), 6.03 (1H, d, J = 2.1 Hz, 6-H), 5.99 (1H, d,
J = 2.2 Hz, 8-H), 3.21 (1H, dd, J = 2.1, 16 9 Hz, H-3a), 2.88 (1H, d,
J = 16.9 Hz, 3-Hb); 13C NMR (125 MHz, (CD3)2CO, 213 K) 195.2,
166.4, 163.9, 160.6, 157.4, 144.3, 129.4, 116.5, 115.5, 112.5,
102.1, 101.8, 96.0, 96.0, 48.6.
3r 82%; 1H NMR (500 MHz, (CD3)2CO, 221 K) 12.16 (1H, s,
5-OH), 10.38 (1H, s, 7-OH), 9.67 (1H, s, 40OH), 7.49 (1H, dd,
J = 2.0, 12.2 Hz, 20-H), 7.39 (1H, dd, J = 1.6, 8.4 Hz, 60-H), 7.08 (1H,
t, J = 8.7 Hz, 50-H), 7.07 (1H, d, J = 2.6 Hz, 2-OH), 6.01 (1H, d,
J = 2.0 Hz, 6-H), 5.99 (1H, d, J = 2.1 Hz, 8-H), 3.28 (1H, dd,
J = 16.9 Hz, H-3a), 2.85 (1H, d, J = 16.9 Hz, 3-Hb); 13C NMR
(125 MHz, (CD3)2CO, 236 K) 195.5, 166.4, 163.8, 160.4, 150.6 (d,
J = 239 Hz), 139.8 (d, J = 5 Hz), 122.0 (d, J = 3 Hz), 117. 2, 113.8 (d,
J = 20 Hz), 101.9, 101.5, 96.0, 95.9, 48.5.
3k 82%; 1H NMR (500 MHz, (CD3)2CO, 220 K) 12.18 (1H, s,
5-OH), 10.52 (1H, s, 7-OH), 7.63 (2H, d, J = 8.7 Hz, 20,60-H), 7.04
(2H, d, J = 8.8 Hz, 30,50-H), 6.99 (1H, s, 2-OH), 6.00 (1H, s, 6-H),
5.99 (1H, s, 8-H), 4.09 (2H, q, J = 7.0 Hz, CH2O), 3.26 (1H, d,
J = 16.9 Hz, H-3a), 2.85 (1H, d, J = 16.9 Hz, 3-Hb), 1.39 (3H, t,
3s 84%; 1H NMR (500 MHz, (CD3)2CO, 221 K) 12.92 (1H, s,
5-OH), 11.18 (1H, s, 7-OH), 8.78 (2H, d, J = 8.1 Hz, 20,60-H), 7.69
(2H, d, J = 8.3 Hz, 30,50-H), 8.10 (1H, s, 2-OH), 6.83 (1H, d,
J = 1.5 Hz, 6-H), 6.80 (1H, d, J = 1.7 Hz, 8-H), 4.13 (1H, d,
Please cite this article in press as: Hao, B., et al. Biosynthesis of natural and novel C-glycosylflavones utilising recombinant Oryza sativa C-glycosyltrans-