4.9. NMR Data of Compounds 1–20
Compound 1: 1H-NMR (400 MHz, CD4O) δH: 6.95 d (1H, H-2′, J = 1.8 Hz), 6.85 dd (1H, H-6′, J = 8.0, 1.8 Hz), 6.80 d (1H, H-5′, J = 8.0 Hz), 5.92 d (1H, H-8, J = 1.9 Hz), 5.88 d (1H, H-6, J = 1.9 Hz), 4.89 d (1H, H-2, J = 12.2 Hz), 4.50 d (1H, H-3, J = 12.2 Hz).
NOESY: nOe signals between H-2/H-3; H-3/H-6′.
Compound 2: 1H-NMR (400 MHz, CD4O) δH: 8.06 d (2H, H-2′, H-6′, J = 8.7 Hz) 6.90 d (2H, H-3′, H-5′, J = 8.7 Hz) 6.40 s (1H, H-8) 6.21 s (1H, H-6) 5.23 d (1H, H-1′′, J = 7.8 Hz) 3.42–3.20 m (3H, H-2′′,3′′,4′′,5′′), 3.69 dd (1H, H-6a′′, J = 12.0, 5.8 Hz) 3.53 dd (1H, H-6b′′ J = 12.0, 2.1 Hz).
13C-NMR (50.3 MHz CD4O) δC: 161.0 (C-2) 100.0 (C-6) 94.4 (C-8) 158.4 (C-9) 104.0 (C-10) 123.0 (C-1′) 131.9 (C-2′,6′) 159.2 (C-4′) 115.1 (C-3′,5′) 103.7 (C-1′′) 76.2 (C-2′′) 78.1a (C-3′′) 71.3 (C-4′′) 78.4a (C-5′′) 62.3 (C-6′′).
a: interchangeable signals.
Compound 3: 1H-NMR (400 MHz, CD4O) δH: 7.93 d (1H, H-2′, J = 2.0 Hz) 7.59 dd (1H, H-6′, J = 8.6, 2.0 Hz) 6.89 d (1H, H-5′, J = 2.0 Hz) 6.19 d (1H, H-6, J = 2.0 Hz) 6.38 d (1H, H-8, J = 2.0 Hz) 3.95 s (3H, OCH3) 5.40 d (1H, H-1′′, J = 7.8 Hz) 3.40–3.20 m (3H, H-2′′,3′′,4′′,5′′) 3.22 dd (1H, H-5′′, J = 4.8, 3.0) 3.73 dd (1H, H-6a′′, J = 12.0, 5.3 Hz) 3.52 dd (1H, H-6b′′, J = 12.0, 1.8 Hz).
13C-NMR (50.3 MHz CD4O) δC: 159.0 (C-2) 100.4 (C-6) 95.2 (C-8) 157.3 (C-9) 104.0 (C-10) 121.0 (C-1′) 114.7 (C-2′) 151.3 (3′) 149.7 (C-4′) 116.4 (C-5′) 103.7 (C-1′′) 123.8 (C-6′) 103.7 (C-1′′) 75.5 (C-2′′) 78.0 (C-3′′) 71.6 (C-4′′) 78.2 (C-5′′) 62.8 (C-6′′).
Compound 4: 1H-NMR (400 MHz, CD4O) δH: 6.82 d (1H, H-2′, J = 1.9 Hz) 6.74 d (1H, H-5′, J = 8.0 Hz) 6.71 dd (1H, H-6′ J = 8.0, 1.9 Hz) 5.82 d (1H, H-6, J = 2.2 Hz) 5.94 d (1H, H-8, J = 2.2 Hz) 4.56 (1H, H-2, J = 7.7 Hz) 3.97 ddq (1H, H-3, J = 8.1, 7.7, 5.4 Hz) 2.84 dd (1H, H-4ax, J = 16.1, 5.4 Hz) 2.50 dd (1H, H-4eq, J = 16.1, 8.1 Hz).
13C-NMR (50.3 MHz CD4O) δC: 82.8 (C-2) 68.8(C-3) 28.4 (C-4) 157.6 (C-5) 95.5 (C-6) 157.8 (C-7) 96.3 (C-8) 156.9 (C-9) 100.8 (C-10) 132.4 (C-1′) 115.3 (C-2′) 146.4 (3′,4′) 116.0 (C-5′) 119.9 (C-6′).
Compound 5: 1H-NMR (400 MHz, CD4O) δH: 8.10 br d (2H, H-2,6, J = 7.7 Hz) 7.50 br t (1H, H-3,5, J = 7.7 Hz) 7.63 (1H, H-4, J = 7.7 Hz). 5.73 d (1H, H-1′, J = 7.6 Hz) 3.52 dd (1H, H-2′, J = 7.6, *Hz) 3.49–3.43 m (3H, H-3′,4′,5′), 3.86 dd (1H, H-6a,′ J = 12.1, 2.1 Hz) 3.71 dd (1H, H-6b′, J = 12.1, 5.1 Hz).
13C-NMR (50.3 MHz CD4O) δC: 133.2 (C-1) 130.7 (C-2,6) 128.4(C-3,5) 132.4 (C-4) 166.2 (C-7) 94.1 (C-1′) 73.4 (C-2′) 77.8a (C-3′) 71.3 (C-4′) 78.4a (C-5′) 62.1 (C-6′).
*: partially overlapped signal; a: interchangeable signals.
Compound 6: 1H-NMR (400 MHz, CD4O) δH: 7.42 br d (2H, H-2,6, J = 7.3 Hz) 7.33 br dd (2H, H-3,5, J = 7.7, 7.3 Hz) 7.28 br d (1H, H-4, J = 7.3 Hz) 4.95 d (1H, H-7a, J = 11.8) 4.69 d (1H, H-7b, J = 11.8 Hz). 4.38 d (1H,H-1′, J = 7.4 Hz) 3.43-3.31 m (3H, H-2′,3′,4′,5′) 3.91 dd (1H, H-6a′, J = 2.1, 1.7 Hz) 3.70 dd (1H, H-6b′, J = 11.7, 5.8 Hz).
13C-NMR (50.3 MHz CD4O) δC: 138.9 (C-1) 128.9 (C-2,6) 128.9 (C-3,5) 128.4 (C-4) 71.4 (C-7) 103.0 (C-1′) 74.9 (C-2′) 78.0a (C-3′) 71.6 (C-4′) 77.9a (C-5′) 62.4 (C-6′).
a: interchangeable signals.
Compound 7: 1H-NMR (400 MHz, CD4O) δH: 7.42 br d (2H, H-2,6, J = 7.3 Hz) 7.33 br dd (2H, H-3,5, J = 7.7, 7.3 Hz) 7.28 br d (1H, H-4, J = 7.3 Hz) 4.87 d (1H, H-7a, J = 11.8) 4.64 d (1H, H-7b, J = 11.8 Hz) 4.32 d (1H,H-1′, J = 7.9 Hz) 3.24 dd (1H, H-2′, J = 8.5, 7.9) 3.70-3.20 m* (3H, H-3′,4′,5′), 3.99 dd (1H, H-6a′, J = 11.7, 1.7 Hz) 3.64 dd (1H, H-6b′, J = 11.3, 5.9 Hz) 4.81 d (1H,H-1′′, J = 1.7 Hz) 3.86 dd (1H, H-2′′ J = 3.1, 1.7 Hz) 3.68 m (3H, H-3′′, J = 9.5 3.1 Hz), 3.34 * (1H H-4′′) 3.67 (1H H-5′′) 1.27 d (3H H-6′′, J = 6.2Hz).
13C-NMR (50.3 MHz CD4O) δC: 128.8 (C-2,6) 128.8 (C-3,5) 128.3 (C-4) 71.4 (C-7) 103.0 (C-1′) 75.0 (C-2′) 77.9a (C-3′) 71.3 (C-4′) 77.4a (C-5′) 67.6 (C-6′) 102.1 (C-1′′) 72.2(C-2′′) 71.1 (C-3′′) 73.7 (C-4′′) 71.1 (C-5′′) 17.9 (C-6′′).
*: partially overlapped signals; a: interchangeable signals.
Compound 8: 1H-NMR (400 MHz, CD4O) δH: 7.14 br d (1H, H-3, J = 8.2 Hz) 7.09-7.07 m (2H, H-4,5) 6.92 dd (1H, H-6, J = 8.2, 1.8 Hz). 4.89* (1H,H-1′) 3.50 (1H, H-2′) 3.82 (-OCH3) 3.48 m (1H, H-3′) 3.40 (1H, H-4′) 3.91 dd (1H, H-6a′, J = 11.7, 1.7 Hz) 3.70 dd (1H, H-6b′, J = 11.7, 5.8 Hz).
13C-NMR (50.3 MHz CD4O) δC: 117.0a (C-3) 112.0 (C-4) 116.8 a (C-5) 120.2 (C-6) –OCH3 (56.1) 102.2 (C-1′) 74.5 (C-2′) 77.5 (C-3′) 71.0 (C-4′) 78.0 (C-5′) 62.0 (C-6′).
*: partially overlapped by methanol-d4 moisture; a: interchangeable signals.
Compound 9: 1H-NMR (400 MHz, CD4O) δH: 6.83 d (1H, H-2, J = 2.8 Hz) 6.86 d (2H, H-5, J = 8.8 Hz) 6.67 dd (1H, H-6, J = 8.8, 2.9 Hz) 3.82 (-OCH3-3), 3.79 (-OCH3-4). 4.79 d (1H, H-1′, J = 7.5 Hz) 3.46–3.35 m (4H, H-2′,3′,4′,5′) 3.91 dd (1H, H-6a′, J = 11.7, 1.7 Hz) 3.70 (1H, H-6b′, J = 11.7, 5.8 Hz).
13C-NMR (50.3 MHz CD4O) δC: 153.9 (C-1) 103.7 (C-2) 145.7 (C-3) 150.6 (C-4) 113.5 (C-5) 109.0 (C-6) –OCH3 (56.1, 57.5) 103.1 (C-1′) 74.9 (C-2′) 77.4a (C-3′) 71.3 (C-4′) 77.9a (C-5′) 62.2 (C-6′).
a: interchangeable signals.
Compound 10: 1H-NMR (400 MHz, CD4O) δH: 7.11 d (2H, H-3,5, J = 8.5 Hz) 7.00 d (2H, H-2,6, J = 8.5 Hz) 2.80–2.76 m (2H, H-7,8) 2.10 s (–CH3). 4.85 d (1H,H-1′, J = 7.8 Hz) 3.43 (1H,H-2′) 3.40–3.30 (2H, H-3′,4′,5′) 3.88 dd (1H, H-6a′, J = 12.0, 1.8 Hz) 3.69 (1H, H-6b′, J = 12.0, 5.0 Hz).
13C-NMR (50.3 MHz CD4O) δC: 157.3 (C-1) 117.5 (C-2,6) 129.0 (C-3,5) 135.3 (C-4) 29.68 (C-7) 45.6 (C-8) 29.63(C-9 –CH3) 210.3 (>C = 0) 102.0 (C-1′) 74.6 (C-2′) 77.8 (C-3′) 71.0 (C-4′) 77.7 (C-5′) 62.0 (C-6′).
Compound 11: 1H-NMR (400 MHz, CD4O) δH: 7.96 d (2H, H-2,6, J = 7.89 Hz).
7.01 d (2H, H-3,5, J = 7.04 Hz) 3.88 s (-OCH3).
13C-NMR (50.3 MHz CD4O) δC: 131.7 (C-2,6) 116.0 (C-3,5) 56.0 (–OCH3).
Compound 12: 1H-NMR (400 MHz, CD4O) δH: 8.06 d (2H, H-2,6, J = 8.1 Hz) 6.90 d (2H, H-3,5, J = 8.1 Hz). 4.96 d (1H,H-1′, J = 7.4 Hz) 3.50–3.30 m (4H, H-2′, 3′, 4′, 5′) 3.91 dd (1H, H-6a′, J = 11.7, 1.7 Hz) 3.70 (1H, H-6b′, J = 11.7, 5.8 Hz).
13C-NMR (50.3 MHz CD4O) δC: 132.0 (C-2,6) 116.2 (C-3,5) 101.0 (C-1′) 75.0 (C-2′) 78.0 (C-3′) 71.8 (C-4′) 78.0 (C-5′) 62.3 (C-6′).
Compound 13: 1H-NMR (400 MHz, CD4O) δH: 7.44 d (2H, H-2,6, J = 8.3 Hz) 6.79 d (2H, H-3,5, J = 8.3 Hz) 7.56 d (1H, H-7, J = 16.0 Hz) 6.29 d (1H, H-8, J = 16.0 Hz).
13C-NMR (200 MHz CD4O) δC: 131.4 (C-2,6) 124.3 (C-3,5) 146.7 (C-7) 115.4 (C-8).
Compound 14: 1H-NMR (400 MHz, CD4O) δH: 7.54 d (2H, H-2,6, J = 7.9 Hz) 7.12 dd (2H, H-3,5, J = 7.9 Hz) 7.60 d (1H, H-7, J = 16.2 Hz) 6.37 d (1H, H-8, J = 16.2 Hz). 4.96 d (1H, H-1′, J = 7.2 Hz) 3.70–3.41 m (4H, H-2′, 3′, 4′, 5′) 3.88 dd (1H, H-6a′, J = 12.1, 2.1) 3.70 (1H, H-6b′, J = 12.1, 8.1 Hz).
13C-NMR (50.3 MHz CD4O) δC: 129.2 (C-1) 132.0 (C-2,6) 117.4 (C-3,5) 159.5 (C-4) 144.7 (C-7) 117.8 (C-8) 170.3 (C-9 –COOH) 101.2 (C-1′) 74.4 (C-2′) 77.5 (C-3′) 70.7 (C-4′) 78.0 (C-5′) 62.2 (C-6′).
Compound 15: 1H-NMR (400 MHz, CD4O) δH: 7.48 d (2H, H-2,6, J = 8.2 Hz) 7.08 d (2H, H-3,5, J = 8.2 Hz) 7.37 d (1H, H-7, J = 16.0 Hz) 6.40 d (1H, H-8, J = 16.0 Hz). 4.94 d (1H, H-1′) 3.55–3.28 m (4H, H-2′,3′,4′,5′) 3.89 dd (1H, H-6a′, J = 11.8, 2.1) 3.70 (1H, H-6b′, J = 11.8, 4.4 Hz).
13C-NMR (50.3 MHz CD4O) δC: 129.4 (C-2, 6) 117.6 (C-3, 5) 139.9 (C-4) 129.9 (C-7) 102.2 (C-1′) 74.3 (C-2′) 77.6 (C-3′) 70.8 (C-4′) 76.5 (C-5′) 62.1 (C-6′).
Compound 16: 1H-NMR (400 MHz, CD4O) δH: 2.45 d (1H, H-2a, J = 17.0 Hz) 2.22 d (1H, H-2b, J = 17.0 Hz) 5.90 tt (1H, H-4, J = 6.9 1.2 Hz) 5.91 d (1H, H-7, J = 15.9 Hz) 6.82 d (1H, H-8, J = 15.9 Hz) 1.89 brs (3H, H-10 CH3) 1.07 s (3H, H-11 CH3) 1.03 s (3H, H-12 CH3) 1.90 d (3H, H-13 CH3 1.2 Hz) 5.63 t (1H, H-14, J = 7.0 Hz) 4.51 dd (1H, H-15a, J = 12.3 7.6 Hz) 4.38 dd (1H, H-15b, J = 12.3 5.9 Hz) 4.28 d (1H, H-1′) 3.17 t (1H, H-2′, J = 8.0 Hz) 3.27–3.35 m (4H, H-3′, 4′, 5′) 3.88 dd (1H, H-6a′, J = 12.0, 1.7) 3.68 (1H, H-6b′, J = 12.0, 5.7 Hz).
13C-NMR (50.3 MHz CD4O) δC: 42.7 (C-1) 49.6 (C-2) 200.0 (C-3 –C=O) 127.4 (C-4) 166.9 (C-5) 80.0 (C-6) 132.0 (C-7) 127.7 (C-8) 136.0 (C-9) 19.4 (C-10) 23.4 (C-11) 24.5 (C-12) 20.4 (C-13) 127.0 (C-14) 65.0 (C-15) 103.0 (C-1′) 74.6 (C-2′) 77.7 (C-3′) 71.3 (C-4′) 77.8 (C-5′) 62.7 (C-6′).
Compound 17: 1H-NMR (400 MHz, CD4O) δH: 8.07 d (2H, H-2′,6′, J = 8.7 Hz) 6.90 d (2H, H-3′,5′, J = 8.7 Hz) 6.34 d (1H, H-8, J = 2.1 Hz) 6.16 d (1H, H-6, J = 2.1 Hz) 5.06 d (1H, H-1′′, J = 7.8 Hz) 3.44 dd (1H, H-2′, J = 7.9, 7.5) 3.43–3.32 m* (3H, H-3′,4′,5′), 3.88 brd (1H, H-6a′, J = 11.0, 1.7 Hz) 3.64 dd (1H, H-6b′, J = 11.0, 5.9 Hz) 4.52 d (1H, H-1′′′ 1.7 Hz) 3.31* (1H, H-2′′′) 3.68 m (2H, H-3′′′, H-5′′′), 3.34* (1H H-4′′′)* 1.27 d (3H H-6′′′, J = 6.2 Hz).
13C-NMR (50.3 MHz CD4O)δC: 159.5 (C-2) 136.1(C-3) 180.2 (C-4) 164.0 (C-5) 100.8 (C-6) 167.1 (C-7) 94.9 (C-8) 159.2 (C-9) 107.5 (C-10) 123.6 (C-1′) 132.2 (C-2′, 6′) 117.0 (C-3′, 5′) 162.2 (C-4′) 101.7 (C-1′′) 76.7 (C-2′′) 78.9 (C-3′′) 72.0a (C-4′′) 78.0 (C-5′′) 69.3 (C-6′′) 102.9 (C-1′′′) 72.9a (C-2′′′) 73.1 (C-3′′′) 74.3 (C-4′′′) 70.5 (C-5′′′) 18.6 (C-6′′′).
*: overlapped signals; a: interchangeable signals.
Compound 18: 1H-NMR (400 MHz, CD4O) δH: 8.04 d (2H, H-2′,6′, J = 8.7 Hz) 6.82 d (2H, H-3′,5′, J = 8.7 Hz) 6.33 d (1H, H-8, J = 2.1 Hz) 6.22 d (1H, H-6, J = 2.1 Hz) 3.94 (3H, –OCH3) 5.84 d (1H, H-1′′, J = 7.8 Hz) 3.24 dd (1H, H-2′′, J = 8.5, 7.9) 3.43–3.32 ma (3H, H-3′′,4′′,5′′), 3.99 dd (1H, H-6a′′, J = 11.7, 1.7 Hz) 3.64 dd (1H, H-6b′′, J = 11.3, 5.9 Hz). 4.51 d (1H, H-1′′′, J = 1.7 Hz) 3.86 dd (1H, H-2′′′, J = 3.1, 1.7 Hz) 3.68 m (3H, H-3′′′, J = 9.5 3.1 Hz), 3.34a (1H H-4′′′) 3.67 (1H H-5′′′) 1.27 d (3H H-6′′′, J = 6.2 Hz).
13C-NMR (50.3 MHz CD4O) δC: 128.8* (C-2′,6′) 128.8 (C-3′,5′) 128.3* (C-4′) 71.4 (C-7)103.0 (C-1′′) 75.0 (C-2′′) 77.9b (C-3′′) 71.3 (C-4′′) 77.4b (C-5′′) 67.6 (C-6′′) 102.1 (C-1′′′) 72.2(C-2′′′) 71.1α (C-3′′′) 73.7 (C-4′′′) 71.1α (C-5′′′) 17.9 (C-6′′′).
a,b: overlapped signals; *: interchanged signals.
Compound 19: δ(ppm) 7.98 d (2H, H-2′, H-6′, J = 8.8 Hz), 7.44 d (1H, H-7′′′, J = 15.6 Hz), 7.36 d (2H, H-2′′′& H-6′′′, J = 9.2 Hz), 6.77 d (2H, d, H-3′ & H-5′, J = 8.8 Hz), 6.77 d (2H, H-3′′′ & H-5′′′, J = 9.2 Hz), 6.37 d (1H, H-8, J = 2.1 Hz), 6.14 d (1H, H-6 J = 2.1 Hz), 6.07 d (1H, H-8′′′, J = 15.6 Hz), 5.20 d (1H, H-1′′, J = 7.6 Hz), 4.35 dd (1H, H-6′′a, J = 12.6, 2.0 Hz), 4.21 dd (1H, H-6′′b, J = 12.8, 6.8 Hz), 3.35–3.51 m (4H, H-2″,3″,4′′,5′′) 159.5 (C-2) 137.0 (C-3) 179.4 (C-4) 162.7 (C-5) 99.7 (C-6) 165.8 (C-7) 94.9 (C-8) 158.3 (C-9) 105.7 (C-10) 123.4 (C-1′) 132.2 (C-2′,6′) 118.0 (C-3′,5′) 161.4 (C-4′) 104.1 (C-1′′) 74.9 (C-2′′) 77.9 (C-3′′) 71.8 (C-4′′) 75.2 (C-5′′) 64.5 (C-6′′) 123.2 (C-1′′′) 131.5 (C-2′′′ ,6′′′) 117.2 (C-3′′′ ,5′′′) 157.5 (C-4′′′) 147.5 (C-7′′′) 115.9 (C-8′′′) 168.7 (C-9′′′).
Compound 20: 7.53 s (2H, H-2,6); 6.42 d (1H, H-8, J = 2 Hz), 6.21 d (1H, H-6, J = 2 Hz), 5.47 d (1H, H-1′′, J = 8 Hz), 3.94 s (6H, OCH3 × 2 at C-3′ and at C-5′) 5.47 d (1H, H-1′′, 7.8 Hz) 3.42–3.20 m (3H, H-2′′,3′′,4′′,5′′), 3.74 dd (1H, H-6a′′ 12.0, 5.8 Hz) 3.58 dd (1H, H-6b′′ 12.0, 2.1 Hz).
13C-NMR (50.3 MHz CD4O) δC: 107.4 (C-2′,6′) 99.6 (C-6) 94.4 (C-8) 56.5 (–OCH3) 102.8 (C-1′′) 76.2 (C-2′′) 78.1a (C-3′′) 71.0 (C-4′′) 77.3a (C-5′′) 62.2 (C-6′′).
a: overlapped signals.