2.4. Spectroscopic Data of Products Obtained in Olefin Cross-Metathesis Reactions
NMR samples of metathesis products contained both E and Z isomers. Analysis was done with the help of 2D NMR spectra: 1H-1H cosy and 1H-13C hetcor.
2.4.1. 1′′,4′′-Bis-(5,4′-dihydroxyisoflavonyl-7-oxy)-but-2′′-en (5)
E Isomer. 1H NMR (300 MHz, D6-DMSO) δ ppm: 12.96 (HO-5, s 2H) 9.64 (HO-4′, s, 2H), 8.40 (H-2; s; 2H) 7.36 (H-2′, H-6′; d; J11,15-12,14 = 8.6 Hz; 4H) 6.80 (H-3′, H-5′; d; J12,14-11,15 = 8.6 Hz; 4H) 6.67 (H-8; d; J5-7 = 2.2 Hz; 2H) 6.42 (H-6; d; J7-5 = 2.2 Hz; 2H) 6.10 (H-2′′, H-3′′; m; 2H) 4.75 (H-1′′, H-4′′; m; 4H).
Z Isomer. 1H NMR (300 MHz, d6-DMSO) δ ppm: 12.93 (H-5; s; 2H) 9.64 (H-4′; s; 2H) 8.38 (H-2; s; 2H) 7.36 (H-2′, H-6′; d; J11,15-12,14 = 8.6 Hz; 4H) 6.80 (H-3′, H-5′; d; J12,14-11,15 = 8.6 Hz; 4H) 6.69 (H-8; d; J5-7 = 2.2 Hz; 2H) 6.45 (H-6; d; J7-5 = 2.2 Hz; 2H) 5.93 (H-2′′, H-3′′; m; 2H) 4.87 (H-1′′, H-4′′; m; 4H).
Due to extremely low solubility of compound 5 we were unable to record 13C NMR and HRMS spectra.
2.4.2. 7′-O-(1′′′-C-(2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3a)
E Isomer. 1H NMR (600 MHz, DMSO-D6) δ ppm: 12.94 (OH-5′; s; 1H) 9.60 (OH-4′′; s; 1H) 8.39 (H-2′; s; 1H) 7.39 (H-2′′, H-6′′; d; J11′-12′,15′-14′ = 8.8 Hz; 2H) 6.83 (H-3′′, H-5′′; d; J12′-11′,14′-15′ = 8.8 Hz; 2H) 6.65 (H-8′; d; J5′-7′ = 2.4 Hz; 1H) 6.40 (H-6′; d; J7′-5′ = 2.4 Hz; 1H) 5.87 (H-3′′′; dt; J3′′-2′′ = 14.6 Hz; J3′′-4′′ = 5.4 × 2 Hz; 1H) 5.81 (H-2′′′; ddd; J2′′-3′′ = 14.6 Hz; J2′′-1L′′ = 6.8 Hz; J2′′-1′′a = 6.3 Hz; 1H) 5.30 (H-3; dd; J3-2 = 8.8 Hz; J3-4 = 8.8 Hz; 1H) 4.91 (H-2; dd; J2-3 = 8.8 Hz; J2-1 = 5.9 Hz; 1H) 4.86 (H-4; dd; J4-3 = 9.1 Hz; J4-5 = 9.1 Hz; 1H) 4.64 (H-4′′; d; J4′′-3′′ = 5.4 Hz; 2H) 4.21–4.13 (H-1, H-6a; m; 2H) 4.00–3.93 (H-5, H-6b; m; 2H) 2.71 (H-1′′′a; m; J1′′a-1′′b = 15.0 Hz; J1′′a-2′′ = 10.9 Hz; J1′′a-1 = 7.6 Hz; 1H) 2.32 (H-1′′′b; m; 1H) 2.03; 2.00; 1.99; 1.98 (CH3–; 12H).
13C NMR (150 MHz, DMSO-D6) δ ppm: 180.37 (C-4′) 170-169 (C=O × 4, C-6′) 164.12 (C-5′) 161.74 (C-4′′) 157.49 (C-8a′) 154.28 (C-2′) 130.67 (C-2′′′) 130.13 (C-2′′, C-6′′) 126.79 (C-3′′′) 122.51 (C-3′) 121.04 (C-1′′) 115.08 (C-3′′, C-5′′) 105.42 (C-4′a) 98.49 (C-8′) 92.96 (C-6′) 71.13 (C-1) 69.81 (C-2) 69.46 (C-3) 68.38 (C-4, C-5) 68.79 (C-4′′′) 61.80 (C-6) 28.42 (C-1′′′) 20.45 (CH3– × 4).
Z Isomer. 1H NMR (600 MHz, DMSO-D6) δ ppm 12.96 (OH-5′; s; 1H) 9.60 (OH-4′′; s; 1H; overlapped) 8.40 (H-2′; s; 1H) 7.39 (H-2′′, H-6′′; 2H; overlapped) 6.83 (H-3′′, H-5′′; 2H; overlapped) 6.69 (H-8′; d; J5′-7′ = 2.35 Hz; 1H) 6.45 (H-6′; d; J7′-5′ = 2.35 Hz; 1H) 5.76 (H-3′′′; dt; J3′′-2′′ = 10.50 Hz; J3′′-4′′ = 5.40 × 2 Hz; 1H) 5.63 (H-2′′′; ddd; J2′′-3′′ = 10.50 Hz; J2′′-1′′b = 6.80 Hz; J2′′-1′′a = 6.30 Hz; 1H) 5.37 (H-3; dd; J3-2 = 9.10 Hz; J3-4 = 9.10 Hz; 1H) 4.94 (H-2; dd; J2-3 = 9.10 Hz; J2-1 = 5.87 Hz; 1H) 4.86 (H-4; 1H; overlapped) 4.80 (H-4′′′; d; J4′′-3′′ = 5.40 Hz; 2H) 4.21–4.13 (H-1, H-6a; m; 2H) 4.00/3.93 (H-5, H-6b; m; 2H) 2.82 (H-1′′′a; m; J1′′a-1′′b = 15.26 Hz; J1′′a-2′′ = 9.39 Hz; J1′′a-1 = 9.39 Hz; 1H) 2.38 (H-1′′′b; m; 1H) 2.02; 2.01; 1.99; 1.98 (CH3–; 12H).
13C NMR (150 MHz, DMSO-D6) δ ppm: 180.37 (C-4′; overlapped) 170-169 (C=O × 4, C-6′) 164.23 (C-5′) 161.74 (C-4′′; overlapped) 157.42 (C-8′a) 154.28 (C-2′; overlapped) 130.13 (C-2′′, C-6′′; overlapped) 129.98 (C-2′′′) 126.00 (C-3′′′) 122.51 (C-3′; overlapped) 121.04 (C-1′′; overlapped) 115.08 (C-3′′, C-5′′; overlapped) 105.42 (C-4′a; overlapped) 98.49 (C-8′; overlapped) 93.12 (C-6′) 71.55 (C-1) 69.90 (C-2) 69.46 (C-3; overlapped) 68.38 (C-4, C-5; overlapped) 64.89 (C-4′′′) 61.80 (C-6; overlapped) 24.58 (C-1′′′) 20.45 (CH3 × 4; overlapped).
HRMS [M + Na]
+. Experimental: 677.1821; calculated: 677.1841.
2.4.3. 1′,4′-Bis-C-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)-but-2′-en (4a)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.50 (H-2′, H-3′; t; 3.8 Hz × 2; 2H) 5.31 (H-3; dd; J3-2 = 9.3 Hz; J3-4 = 8.9 Hz; 2H) 5.07 (H-2; dd; J2-3 = 9.3 Hz; J2-1 = 5.4 Hz; 2H) 5.00 (H-4; dd; J4-3 = 8.9 Hz; J4-5 = 8.9 Hz; 2H) 4.26 (H-6a; dd; J6a-6b = 12.2 Hz; J6a-5 = 5.0 Hz; 2H) 4.21 (H-1; ddd; J1-1′a = 10.5 Hz, J1-2 = 5.4 Hz; J1-1′b = 4.9 Hz; 2H) 4.06 (H-6b; dd; J6b-6a = 12.2 Hz; J6b-5 = 2.9 Hz; 2H) 3.85 (H-5; ddd; J5-4 = 8.9 Hz; J5-6a = 5.0 Hz; J5-6b = 2.9 Hz; 2H) 2.52 (H-1′a, H-4′a; ddd; J1′a-1′b = 15.0 Hz; J1′a-1 = 10.5 Hz; J = 4.0 Hz; 2H) 2.28 (H-1′b, H-4′b; ddd; J1′b-1′a = 15.0 Hz; J1′b-1 = 4.9 Hz; J = 4.0 Hz; 2H) 2.09 (OAc; s; 6H) 2.06 (OAc; s; 6H) 2.04 (OAc; s; 12H).
13C NMR (75 MHz, CDCl3) δ ppm: 170.62 (C=O) 170.08 (C=O) 169.57 (C=O) 169.46 (C=O) 127.82 (C-2′, C-3′) 72.06 (C-1) 70.19 (C-2) 70.06 (C-3) 68.87 (C-4) 68.60 (C-5) 62.07 (C-6) 29.33 (C-1′, C-4′) 20.69/20.63 (CH3).
Z Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 5.52 (H-2′, H-3′; t; 4.4 Hz × 2; 2H).
13C NMR (150 MHz, CDCl3) δ ppm: 170.40 (C=O) 170.03 (C=O) 169.63 (C=O) 69.53 (C=O) 126.52 (C-2′, C-3′) 72.06 (C-1, overlapped) 70.19 (C-2, overlapped) 70.06 (C-3, overlapped) 69.17 (C-4) 68.70 (C-5) 61.99 (C-6) 24.56 (C-1′, C-4′) 20.69/20.63 (CH3).
HRMS [M + Na]
+. Experimental: 739.2404; calculated: 739.2420.
2.4.4. 7′-O-(1′′′-C-(2,3,4,6-Tetra-O-acetyl-α-D-galactopyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3b)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 12.81 (H-5′; s; 1H) 7.84 (H-2′; s; 1H) 7.36 (H-2′′, H-6′′; d; J11′,15′-12′,14′ = 8.6 Hz; 2H) 6.87 (H-3′′, H-5′′; d; J12′,14′-11′,15′ = 8.6 Hz; 2H) 6.37 (H-8′; d; J5′-7′ = 2.2 Hz; 1H) 6.34 (H-6′; d; J7′-5′ = 2.2 Hz; 1H) 5.82/5.78 (H-2′′′, H-3′′′; m; 2H) 5.44 (H-4; dd; J4-5 = J4-3 = 2.4 Hz; 1H) 5.30/5.21 (H-2, H-3; m; 2H) 4.52 (H-4′′′; d; J4′′-3′′ = 3.7 Hz; 2H) 4.36–4.28 (H-1, H-6a; m; 2H) 4.13–4.05 (H-5, H-6b; m; 2H) 2.61–2.28 (H-1′′′a, H-1′′′b; m; 2H) 2.13 (CH3; s; 3H) 2.10 (CH3; s; 3H) 2.06 (CH3; s; 3H) 2.05 (CH3; s; 3H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.63 (CH3) 20.72 (CH3 × 2) 20.76 (CH3) 29.65 (C-1′′′) 61.20 (C-6) 67.37 (C-5) 67.85 (C-4′′′) 68.26 (C-3) 68.49 (C-4) 68.70 (C-2) 71.19 (C-1) 92.99 (C-8′) 98.69 (C-6′) 106.24 (C-4′a) 115.59 (C-3′′, C-5′′) 122.58 (C-3′) 123.66 (C-1′′) 126.97 (C-3′′′) 130.16 (C-2′′′) 130.24 (C-2′′, C-6′′) 152.76 (C-2′) 156.28 (C-4′′) 157.84 (C-8′a) 162.56 (C-5′) 164.36 (C-7′) 169.92 (C=O) 170.06 (C=O) 170.14 (C=O) 170.72 (C=O) 180.86 (C-4′).
Z Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 12.81 (H-5′; overlapped; 1H) 7.85 (H-2′; s; 1H) 7.36 (H-2′′, H-6′′; overlapped; 2H) 6.87 (H-3′′, H-5′′; overlapped; 2H) 6.41 (H-8′; d; J5′-7′ = 2.2 Hz; 1H) 6.37 (H-6′; overlapped; 1H) 5.87–5.78 (H-3′′′; m; 1H) 5.71 (H-2′′′; dt; J2′′-3′′ = 11.4; J2′′-1′′ = 7.5 × 2 Hz; 1H) 5.44 (H-4; overlapped; 1H) 5.30–5.21 (H-2, H-3; overlapped; 2H) 4.62 (H-4′′′; d; J4′′-3′′ = 5.9 Hz; 2H) 4.36–4.28 (H-1, H-6a; overlapped; 2H) 4.13–4.05 (H-5, H-6b; overlapped; 2H) 2.61–2.28 (H-1′′′a, H-1′′′b; overlapped; 2H) 2.13-2.05 (CH3; overlapped; 12H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.63/20.76 (CH3) 25.55 (C-1′′′) 61.06 (C-6) 64.43 (C-4′′′) 67.25 (C-5) 67.85 (C-3) 68.43 (C-4) 68.83 (C-2) 71.19 (C-1; overlapped) 92.99 (C-8′; overlapped) 98.72 (C-6′) 106.30 (C-4′a) 115.59 (C-3′′, C-5′′; overlapped) 122.58 (C-3′; overlapped) 123.69 (C-1′′) 126.25 (C-3′′′) 129.47 (C-2′′′) 130.24 (C-2′′, C-6′′; overlapped) 152.76 (C-2′; overlapped) 156.28 (C-4′′; overlapped) 157.87 (C-8′a) 162.59 (C-5′) 164.36 (C-7′; overlapped) 169.92 (C=O; overlapped) 170.00 (C=O) 170.10 (C=O) 170.76 (C=O) 180.86 (C-4′; overlapped).
HRMS [M + Na]
+. Experimental: 677.1819; calculated: 677.1841.
2.4.5. 1′,4′-Bis-C-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-but-2′-en (4b)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.48 (H-2′, H-3′; t; 3.7 Hz × 2; 2H) 5.41 (H-4; dd; J4-3 = J4-5 = 2.7 Hz; 2H) 5.26/5.22 (H-2; m; 2H) 5.19 (H-3; dd; J3-4 = 2.7; J3-2 = 9.1 Hz; 2H) 4.34/4.19 (H-1, H-6a; m; 4H) 4.11/4.02 (H-5, H-6b; m; 4H) 2.48/2.38 (H-1′a, H-4′a; m; 2H) 2.28/2.18 (H-1′b, H-4′b; m; 4H) 2.12 (CH3; s; 6H) 2.08 (CH3; s; 6H) 2.06 (CH3; s; 6H) 2.04 (CH3; s; 6H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.65 (CH3) 20.73 (CH3) 20.77 (CH3) 29.67 (C-1′, C-4′) 60.98 (C-6) 67.28 (C-5) 67.83 (C-3) 68.23 (C-2) 68.43 (C-4) 71.38 (C-1) 128.03 (C-2′, C-3′) 169.75 (C=O) 169.89 (C=O) 170.05 (C=O) 170.51 (C=O).
Z Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.51 (H-2′, H-3′; t; 4.4 Hz × 2). Only H-2′ and H-3′ signals of Z isomer were not overlapped by signals of isomer E.
13C NMR (75 MHz, CDCl3) δ ppm: 20.65/20.77 (CH3) 24.81 (C-1′, C-4′) 61.13 (C-6) 67.36 (C-5) 67.83 (C-3) 68.50 (C-2) 68.64 (C-4) 71.38 (C-1) 126.77 (C-2′, C-3′) 169.85 (C=O × 2) 170.02 (C=O) 170.59 (C=O).
HRMS [M + Na]
+. Experimental: 739.2416; calculated: 739.2420.
2.4.6. 7′-O-(1′′′-C-(2,3,4,6-Tetra-O-acetyl-α-D-mannopyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3c)
E Isomer. 1H NMR (600 MHz, d6-DMSO) δ ppm: 12.91 (H-5′; s; 1H) 9.62 (H-4′′; s; 1H) 8.34 (H-2′; s; 1H) 7.37 (H-2′′, H-6′′; dd; J11′15′-12′,14′ = 8.6 Hz; J11′-15′ = 2.2 Hz; 2H) 6.81 (H-3′′, H-5′′; dd; J12′14′-11′,15′ = 8.5 Hz; J12′-14′ = 2.2 Hz; 2H) 6.60 (H-8′; d; J5′-7′ = 2.2 Hz; 1H) 6.36 (H-6′; d; J7′-5′ = 2.2 Hz; 1H) 5.84 (H-3′′′; dt; J3′′-2′′ = 15.5 Hz; J3′′-4′′ = 5.4 × 2 Hz; 1H) 5.79 (H-2′′′; ddd; J2′′-3′′ = 15.5 Hz; J2′′-1′′a = 6.4 Hz; J2′′-1′′b = 6.4 Hz; 1H) 5.24 (H-3; dd; J3-4 = 9.0 Hz; J3-2 = 3.3 Hz; 1H) 5.07 (H-2; dd; J2-1 = 3.3 Hz; J2-3 = 3.3 Hz; 1H) 5.02 (H-4; dd; J4-5 = J4-3 = 8.5 Hz; 1H) 4.61 (H-4′′′; d; J4′′-3′′ = 5.4 Hz; 2H) 4.20 (H-6a; dd; J6a-6b = 12.2 Hz; J6a-5 = 6. Hz; 1H) 3.99/3.93 (H-1, H-5, H-6b; m; 3H) 2.69/2.59 (H-1′′′a; m; 1H) 2.43 (H-1′′′b; ddd; J1′′b-1′′a = 14.6 Hz; J1′′b-2′′ = 6.4 Hz; J1′′b-1 = 5.8 Hz; 1H).
13C NMR (150 MHz, d6-DMSO) δ ppm: 20.46 (CH3) 20.49 (CH3) 20.54 (CH3) 20.68 (CH3) 31.26 (C-1′′′) 61.90 (C-6) 64.90 (C-4′′′) 66.66 (C-4) 68.30 (C-3) 69.79 (C-2) 69.83 (C-5) 73.37 (C-1) 93.01 (C-8′) 98.55 (C-6′) 105.48 (C-4′a) 115.14 (C-3′′, C-5′′) 121.10 (C-3′) 122.56 (C-1′′) 127.09 (C-3′′′) 130.17 (C-2′′, C-6′′, C-2′′′) 154.28 (C-2′) 157.50 (C-4′′, C-8′a) 161.75 (C-5′) 164.15 (C-7′) 169.56 (C=O × 2) 169.77 (C=O) 170.08 (C=O) 180.41 (C-4′).
Z Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 12.82 (H-5′; s; 1H) 7.85 (H-2′; s; 1H) 7.39 (H-2′′, H-6′′; d; J11′,15′-12′,14′ = 8.7 Hz; 2H) 6.89 (H-3′′, H-5′′; d; J11′,15′-12′,14′ = 8.7 Hz; 2H) 6.43 (H-8′; d; J5′-7′ = 2.4 Hz; 1H) 6.40 (H-6′; d; J7′-5′ = 2.4 Hz; 1H) 5.86 (H-3′′′; ddd; J3′′-2′′ = 11.0 Hz; J3′′-4′′a = J3′′-4′′b = 6.3 Hz; J3′′-1′′a = J3′′-1′′b = −1.4 Hz; 1H) 5.73 (H-2′′′; ddd; J2′′-3′′ = 11.0 Hz; J2′′-1′′a = J2′′-1′′b = 7.3; J2′′-4′′a = J2′′-4′′b = −1.3 Hz; 1H) 5.28 (H-3; dd; J3-4 = 8.2 Hz; J3-2 = 3.4 Hz; 1H) 5.20 (H-2; dd; J2-1 = 4.1 Hz; J2-3 = 3.4 Hz; 1H) 5.18 (H-4; dd; J4-3 = 8.2 Hz; J4-5 = 7.6 Hz; 1H) 4.68 (H-4′′′a; ddd; J4′′a-4′′b = 12.3 Hz; J4′′a-3′′ = 6.3 Hz; J4′′a-2′′ = −1.3 Hz; 1H) 4.65 (H-4′′′b; ddd; J4′′b-4′′a = 12.3 Hz; J4′′b-3′′ = 6.3 Hz; J4′′b-2′′ = −1.3 Hz; 1H); 4.42 (H-6a; dd; J6a-6b = 12.1 Hz; J6a-5 = 6.7 Hz; 1H) 4.12 (H-6b; dd; J6b-6a = 12.1 Hz; J6b-5 = 3.3 Hz; 1H) 4.06 (H-1; ddd; J1-1′′a = 8.7; J1-1′′b = 5.9 Hz; J1-2 = 4.1 Hz; 1H) 2.58 (H-1′′′a; dddd; J1′′a-1′′b = 15.0 Hz; J1′′a-1 = 8.7 Hz; J1′′a-2′′ = 7.3 Hz; J1′′a-3′′ = −1.4 Hz; 1H) 2.53 (H-1′′′b; dddd; J1′′a-1′′b = 15.0 Hz; J1′′a-1 = 5.9; J1′′a-2′′ = 7.3 Hz; J1′′a-3′′ = −1.4 Hz; 1H) 2.12 (CH3; s; 3H) 2.09 (CH3; s; 6H) 2.06 (CH3; s; 3H).
13C NMR (150 MHz, CDCl3) δ ppm: 20.74 (CH3) 20.78 (CH3) 20.81 (CH3) 20.93 (CH3) 28.23 (C-1′′′) 62.05 (C-6) 64.50 (C-4′′′) 67.13 (C-4) 68.59 (C-3) 69.72 (C-2) 71.33 (C-5) 73.33 (C-1) 93.10 (C-8′) 98.81 (C-6′) 106.39 (C-4′a) 115.60 (C-3′′, C-5′′) 122.95 (C-3′) 123.70 (C-1′′) 126.94 (C-3′′′) 128.69 (C-2′′′) 130.32 (C-2′′, C-6′′) 152.74 (C-2′) 156.04 (C-4′′) 157.92 (C-8′a) 162.73 (C-5′) 164.43 (C-7′) 169.70 (C=O) 169.96 (C=O) 170.21 (C=O) 170.72 (C=O) 180.86 (C-4′).
HRMS [M + Na]
+. Experimental: 677.1805; calculated: 677.1841.
2.4.7. 1′,4′-Bis-C-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)-but-2′-en (4c)
Signals of Z isomer were completely overlapped by signals of isomer E.
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.57 (H-2′, H-3′; t; 3.3 Hz × 2; 2H) 5.27/5.17 (H-2, H-3, H-4; m; 6H) 4.34 (H-6a; dd; J6a-6b = 12.0 Hz; J6a-5 = 5.8 Hz; 2H) 4.10 (H-6b; dd; J6b-6a = 12.0 Hz; J6b-5 = 3.0 Hz; 2H) 4.00 (H-1; ddd; J1-1′a = 7.2 Hz; J1-1′a = 7. Hz; J1-1′a= 2.9 Hz; 2H) 3.9 (H-5; ddd; J5-4 = 6.3 Hz; J5-6a = 5.8 Hz; J5-6b = 3.0 Hz; 2H) 2.54/2.36 (H-1′a, H-1′b, H-4′a, H-4′b; m; 4H) 2.12 (CH3; s; 6H) 2.10 (CH3; s; 6H) 2.07 (CH3; s; 6H) 2.03 (CH3; s; 6H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.94 (CH3) 20.77 (CH3 × 2) 20.70 (CH3) 32.50 (C-1′, C-4′) 62.34 (C-6) 66.93 (C-4) 68.69 (C-3) 69.82 (C-2) 70.72 (C-5) 74.29 (C-1) 128.00 (C-2′, C-3′) 169.64 (C=O) 169.95 (C=O) 170.14 (C=O) 170.66 (C=O).
HRMS [M + Na]
+. Experimental: 739.2433; calculated: 739.2420.
2.4.8. 7′-O-(1′′′-C-(2,3,4,6-Tetra-O-benzyl-α-D-glucopyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3d)
E Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 12.80 (OH-5′; s; 1H) 7.77 (H-2′; s; 1H) 7.33/7.11 (–Ph, H-2′′, H-6′′; m; 22H) 6.82 (H-3′′, H-5′′; d; J12′-11′,14′-15′ = 8.2 Hz; 2H) 6.32 (H-8′; d; J5′-7′ = 2.4 Hz; 1H) 6.31 (H-6′; d; J7′-5′ = 2.4 Hz; 1H) 5.83 (H-2′′′; d; J2′′-3′′ = 15.6; J2′′-1′′a = 7.0 Hz; J2′′-1′′b = 7.0 Hz; 1H) 5.68 (H-3′′′; dt; J3′′-2′′ = 15.6 Hz; J3′′-4′′ = 5.9 Hz × 2; 1H) 4.94 (–OCH2Ph; d; Jgem = 10.9; 1H) 4.82 (–OCH2Ph; d; Jgem = 10.6; 1H) 4.81 (–OCH2Ph; d; Jgem = 10.9 Hz; 1H) 4.70 (–OCH2Ph; d; Jgem = 11.7 Hz; 1H) 4.61 (–OCH2Ph; d; Jgem = 11.7 Hz; 1H) 4.59 (–OCH2Ph; d; Jgem = 12.2 Hz; 1H) 4.47 (–OCH2Ph; d; Jgem = 10.6 Hz; 1H) 4.46 (–OCH2Ph; d; Jgem = 12.2 Hz; 1H) 4.40 (H-4′′′; d; J4′′-3′′ = 5.9 Hz; 2H) 4.13 (H-1; ddd; J1-2 = 5.2; J1-1′′a = 10.6 Hz; J1-1′′b = 5.0 Hz; 1H) 3.81 (H-3; J3-2 = 9.4 Hz; J3-4 = 7.9 Hz; 1H) 3.76 (H-2; dd; J2-3 = 9.4 Hz; J2-1 = 5.7 Hz; 1H) 3.71–3.66 (H-6a; m; 1H) 3.65/3.59 (H-4, H-5, H-6b; m; 3H) 2.53 (H-1′′′a, H-1′′′b; m; 2H).
13C NMR (150 MHz, CDCl3) δ ppm: 180.79 (C-4′) 164.53 (C-7′) 162.48 (C-8′a) 157.81 (C-5′) 156.21 (C-4′′) 152.65 (C-2′) 138.59 (Ph) 138.05 (Ph) 137.92 (Ph) 137.83 (Ph) 131.83 (C-2′′′) 130.18 (C-2′′, C-6′′) 128.45/127.60 (Ph × 4) 126.19 (C-3′′′) 123.58 (C-3′) 122.59 (C-1′′) 115.62 (C-3′′, C-5′′) 106.14 (C-4′a) 98.82 (C-6′) 92.95 (C-8′) 82.18 (C-3) 79.90 (C-2) 78.07 (C-4) 75.43 (CH2Ph) 75.13 (CH2Ph) 73.52 (C-1) 73.43 (CH2Ph) 73.16 (CH2Ph) 71.18 (C-5) 68.93 (C-6) 68.97 (C-4′′′) 28.43 (C-1′′′).
Z Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 12.79 (OH-5′; s; 1H) 7.77 (H-2′; s; 1H; overlapped) 7.33/7.11 (–Ph, H-2′′, H-6′′; m; 22H; overlapped) 6.82 (H-3′′, H-5′′; 2H; overlapped) 6.35 (H-8′; d; J5′-7′ = 2.35 Hz; 1H) 6.34 (H-6′; d; J7′-5′ = 2.35 Hz; 1H) 5.77 (H-2′′′, H-3′′′; m; 2H) 4.93 (–OCH2Ph; d; Jgem = 10.86 Hz; 1H) 4.82 (–OCH2Ph; d; Jgem = 10.56 Hz; 1H) 4.81 (–OCH2Ph; 1H; overlapped) 4.71 (–OCH2Ph; d; Jgem = 11.44 Hz; 1H) 4.60 (–OCH2Ph; d; Jgem = 11.74 Hz; 1H) 4.60 (–OCH2Ph; d; Jgem = 12.03 Hz; 1H) 4.47 (–OCH2Ph; 1H; overlapped) 4.46 (–OCH2Ph; 1H; overlapped) 4.58 (H-4′′′; 2H; overlapped) 4.13 (H-1; ddd; J1-2 = 5.21; J1-1′′a = 10.64 Hz; J1-1′′b = 5.0 Hz; 1H) 3.81 (H-3; 1H; overlapped) 3.76 (H-2; 1H; overlapped) 3.71/3.66 (H-6a; 1H; overlapped) 3.65/3.59 (H-4, H-5, H-6b; 3H; overlapped) 2.53 (H-1′′′a, H-1′′′b; 2H; overlapped).
13C NMR (150 MHz, CDCl3) δ ppm: 180.83 (C-4′) 164.51 (C-7′) 162.55 (C-8′a) 157.84 (C-5′) 156.16 (C-4′′) 152.68 (C-2′) 138.59–137.83 (Ph × 4; overlapped) 130.94 (C-2′′′) 130.18 (C-2′′, C-6′′; overlapped) 128.45–127.60 (Ph × 4) 125.51 (C-3′′′) 123.62 (C-3′) 122.63 (C-1′′) 115.62 (C-3′′, C-5′′; overlapped) 106.23 (C-4′a) 98.83 (C-6′) 92.98 (C-8′) 82.12 (C-3) 79.82 (C-2) 77.91 (C-4) 75.40 (CH2Ph) 75.05 (CH2Ph) 73.89 (C-1) 73.48 (CH2Ph) 73.32 (CH2Ph) 71.55 (C-5) 68.87 (C-6) 64.59 (C-4′′′) 24.14 (C-1′′′).
2.4.9. 1′,4′-Bis-C-(2,3,4,6-tetra-O-benzylo-α-D-glukopyranosyl)-but-2′-en (4d)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 7.09/7.34 (Ph; m; 40H) 5.51 (H-2′, H-3′; t; 3.5 Hz × 2; 2H) 4.94/4.41 (CH2Ph; m; 16H) 4.07 (H-1; ddd; J1-2 = 5.6 Hz; J1-1′a = 9.0 Hz; J1-1′b = 4.6 Hz; 2H) 3.84/3.54 (H-2, H-3, H-4, H-5, H-6a, H-6b; m; 12H) 2.50/2.41 (H-1′a, H-1′b, H-4′a, H-4′b; m; 4H).
Z Isomer. 1H NMR (75 MHz, CDCl3) δ ppm: 5.56 (H-2′, H-3′; t; 4.0 Hz × 2; 2H). Only H-2′ and H-3′ signals were not overlapped by signals of E isomer.
2.4.10. 7′-O-(1′′′-C-(3,4,6-Tri-O-acetyl-2-deoxy-α-D-glucopyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3e)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 12.81 (H-5′; s; 1H) 7.83 (H-2′; s; 1H) 7.35 (H-2′′, H-6′′; d; J11′,15′-12′,14′ = 8.5 Hz; 2H) 6.86 (H-3′′, H-5′′; d; J12′,14′-11′,15′ = 8.5 Hz; 2H) 6.37 (H-8′; d; J5′-7′ = 2.1 Hz; 1H) 6.34 (H-6′; d; J7′-5′ = 2.1 Hz; 1H) 5.82 (H-2′′′; dddt; J2′′-3′′ = 15.6 Hz; J2′′-1′′a = J2′′-1′′b = 7.1 Hz; J2′′-4′′ = −1.5 × 2; 1H) 5.79 (H-3′′′; dtd; J3′′-2′′ = 15.6 Hz; J3′′-4′′ = 5.4 × 2; J3′′-1′′a = J3′′-1′′b = −1.5 Hz; 1H) 5.14 (H-3; ddd; J3-2b = 7.6 Hz; J3-4 = 7.0 Hz; J3-2a = 4.6 Hz; 1H) 4.89 (H-4; dd; J4-3 = J4-5 = 7.0 Hz; 1H) 4.51 (H-4′′′; d; J4′′-3′′ = 3.7 Hz; 2H) 4.43 (H-6a; dd; J6a-6b = 12.1 Hz; J6a-5 = 6.2 Hz; 1H) 4.12–4.06 (H-1, H-6b; m; 2H) 3.94 (H-5; ddd; J5-4 = 7.0 Hz; J5-6a = 6.2 Hz; J5-6b = 3.4 Hz; 1H) 2.56 (H-1′′′a; dddd; J1′′a-1′′b = −13.0 Hz; J1′′a-1 = 8.5; J1′′a-2′′ = 7.1 Hz; J1′′a-2′′ = −1.5 Hz; 1H) 2.34 (H-1′′′b; dddd; J1′′b-1′′a = −13.0 Hz; J1′′b-1 = 5.2 Hz; J1′′b-2′′ = 7.1 Hz; J1′′b-3′′ = −1.5 Hz; 1H) 2.10 (CH3; s; 3H) 2.08 (CH3; s; 3H) 2.08 (CH3; s; 3H) 2.00 (H-2a; ddd; J2a-2b = 14.0 Hz; J2a-1 = 4.8 Hz; J2a-3 = 4.6 Hz; 1H) 1.90–1.82 (H-2b; m; 1H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.77 (CH3) 20.80 (CH3) 21.02 (CH3) 31.97 (C-2) 35.32 (C-1′′′) 61.91 (C-6) 68.36 (C-4) 68.56 (C-3) 68.72 (C-4′′′) 69.42 (C-1) 70.91 (C-5) 93.04 (C-8′) 98.70 (C-6′) 106.19 (C-4′a) 115.59 (C-3′′, C-5′′) 122.47 (C-3′) 123.63 (C-1′′) 126.85 (C-3′′′) 130.63 (C-2′′′) 130.20 (C-2′′, C-6′′) 152.74 (C-2′) 156.34 (C-4′′) 157.81 (C-8′a) 162.51 (C-5′) 164.39 (C-7′) 169.57 (C=O) 170.22 (C=O) 170.95 (C=O) 180.85 (C-4′).
Z Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 12.81 (H-5′; s; 1H) 7.84 (H-2′; s; 1H) 7.35 (H-2′′, H-6′′; overlapped; 2H) 6.86 (H-3′′, H-5′′; overlapped; 2H) 6.42 (H-8′; d; J5′-7′ = 2.1 Hz; 1H) 6.38 (H-6′; d; J7′-5′ = 2.1 Hz; 1H) 5.85–5.79 (H-3′′′; overlapped; 1H) 5.72 (H-2′′′; ddd; J2′′-3′′ = 10.9 Hz; J2′′-1′′a = J2′′-1′′b = 7.3 Hz; 1H) 5.14 (H-3; overlapped; 1H) 4.88 (H-4; dd; J4-3 = J4-5 = 6.6 Hz; 1H) 4.64 (H-4′′′; d; J4′′-3′′ = 5.8 Hz; 2H) 4.48 (H-6a; dd; J6a-6b = 11.9 Hz; J6a-5 = 6.9 Hz; 1H) 4.12–4.06 (H-1, H-6b; m; 2H) 3.96 (H-5; partially overlapped; 1H) 2.60–2.51 (H-1′′′a; overlapped; 1H) 2.40 (H-1′′′b; dd; partially overlapped; J1′′b-2′′ = 7.3; J1′′b-1 = 6.0 Hz; 1H) 2.10–2.08 (CH3; zakryte; 9H) 2.00 (H-2a; overlapped; 1H) 1.90–1.82 (H-2b; overlapped; 1H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.77 (CH3; overlapped) 20.80 (CH3; overlapped) 21.02 (CH3; overlapped) 31.13 (C-1′′′) 31.88 (C-2) 61.78 (C-6) 64.47 (C-4′′′) 68.17 (C-4) 68.52 (C-3) 69.20 (C-1) 71.22 (C-5) 93.04 (C-8′; overlapped) 98.74 (C-6′) 106.23 (C-4′a) 115.59 (C-3′′, C-5′′; overlapped) 122.47 (C-3′; overlapped) 123.63 (C-1′′; overlapped) 126.27 (C-3′′′) 129.73 (C-2′′′) 130.20 (C-2′′, C-6′′; overlapped) 152.74 (C-2′; overlapped) 156.34 (C-4′′; overlapped) 157.84 (C-8′a) 162.51 (C-5′; overlapped) 164.42 (C-7′) 169.57 (C=O; overlapped) 170.22 (C=O; overlapped) 170.95 (C=O; overlapped) 180.85 (C-4′; overlapped).
HRMS [M + Na]
+. Experimental: 619.1772; calculated: 619.1786.
2.4.11. 1′,4′-Bis-C-(2,3,4,6-tetra-O-acetyl-2-deoxy-α-D-glucopyranosyl)-but-2′-en (4e)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.57 (H-2′, H-3′; m; 2H) 5.11 (H-3; ddd; J3-4 = 7.3 Hz; J3-2a = 4.5 Hz; J3-2b = 8.0 Hz; 2H) 4.88 (H-4; dd; J4-5 = J4-3 = 7.3 Hz; 2H) 4.39 (H-6a; dd; J6a-6b = 12.0 Hz; J6a-5 = 5.9 Hz; 2H) 4.07 (H-6b; dd; J6b-6a = 12.0 Hz; J6b-5 = 3.2 Hz; 2H) 4.07/3.98 (H-1; m; 2H) 3.89 (H-5; ddd; J5-4 = 7.3; J5-6a = 5.9; J5-6b = 3.2 Hz; 2H) 2.51/2.22 (H-1′a, H-1′b, H-4′a, H-4′b; m; 4H) 2.09 (CH3; s; 6H) 2.07 (CH3; s; 6H) 2.06 (CH3; s; 6H) 2.02/1.93 (H-2a; m; 2H) 1.90/1.79 (H-2b; m; 2H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.80 (CH3) 20.83 (CH3) 21.04 (CH3) 35.56 (C-1′, C-4′) 31.92 (C-2) 62.06 (C-6) 68.58 (C-4) 68.66 (C-3) 70.09 (C-1) 70.73 (C-5) 128.46 (C-2′, C-3′) 169.75 (C=O) 170.03 (C=O) 170.73 (C=O).
Z Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.57 (H-2′, H-3′; overlapped; 2H) 5.14 (H-3; partially overlapped; 2H) 4.87 (H-4; dd; J4-5 = J4-3 = 7.0 Hz; 2H) 4.42 (H-6a; dd; J6a-6b = 12.0 Hz; J6a-5 = 6.4 Hz; 2H) 4.1/4.05 (H-6b; overlapped; 2H) 4.07/3.98 (H-1; overlapped; 2H) 3.92 (H-5; ddd; J5-4 = 7.0; J5-6a = 6.4 Hz; J5-6b = 3.4 Hz; 2H) 2.51/2.22 (H-1′a, H-1′b, H-4′a, H-4′b; partially overlapped; 4H) 2.09/2.06 (CH3; overlapped; 18H) 2.02/1.93 (H-2a; overlapped; 2H) 1.90/1.79 (H-2b; overlapped; 2H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.80/21.04 (CH3) 30.56 (C-1′, C-4′) 32.00 (C-2) 61.98 (C-6) 68.47 (C-4) 68.66 (C-3) 69.84 (C-1) 70.99 (C-5) 127.10 (C-2′, C-3′) 169.75/170.73 (C=O).
HRMS [M + Na]
+. Experimental: 623.2328; calculated: 623.2310.
2.4.12. 7′-O-(1′′′-C-(4-O-Acetyl-2,3,6-trideoxy-α-L-erythro-heks-2-enpyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3f)
E Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 12.80 (OH-5; s; 1H) 7.82 (H-2′; s; 1H) 7.34 (H-2′′, H-6′′; d; J10′-11′,14′-13′ = 8.63 Hz; 2H) 6.85 (H-3′′, H-5′′; d; J11′-10′,13′-14′ = 8.63 Hz; 2H) 6.36 (H-8′; d; J7′-5′ = 1.99 Hz; 1H) 6.39 (H-6′; d; J5′-7′ = 2.65 Hz; 1H) 5.92 (H-2′′′; ddd; J2′′-3′′ = 15.1; J2′′-1′′a = J2′′-1′′b = 7.3 Hz; 1H) 5.94–5.92 (H-2; m; 1H) 5.82 (H-3; ddd; J3-2 = 10.1 Hz; J3-4 = 3.5; J3-1 = 1.7 Hz; 1H) 5.79 (H-3′′′; dt; J3′′-2′′ = 15.1 Hz; J3′′-4′′ = 6.0 Hz × 2; 1H) 4.91 (H-4; broad signal; 1H) 4.53 (H-4′′′; d; J4′′-3′′ = 6.0 Hz; 2H) 4.26 (H-1; ddd; J1-1′′a = J1-1′′b = 7.3 Hz; J1-2 = 1.99 Hz; 1H) 3.96 (H-5; dq; J5-6 = 6.63 Hz × 3; J5-4 = 4.64 Hz; 1H) 2.49 (H-1′′′a; ddd; J1′′a-1′′b = 14.60 Hz; J1′′a-1 = J1′′a-2′′ = 7.30 Hz; 1H) 2.38 (H-1′′′b; ddd; J1′′b-1′′a = 14.60 Hz; J1′′b-1 = J1′′b-2′′ = 7.30 Hz; 1H) 2.10 (OAc; s; 3H) 1.26 (H-6; t; J6-5 = 6.63 Hz × 3; 3H).
13C NMR (75 MHz, CDCl3) δ ppm: 180.87 (C-4′) 170.07 (C=O) 164.46 (C-7′) 162.42 (C-5′) 157.81 (C-4′′) 156.39 (C-8′a) 152.77 (C-2′) 33.20 (C-2) 131.38 (C-2′′′) 130.15 (C-2′′, C-6′′) 126.60 (C-3′′′) 123.65 (C-3′) 123.06 (C-3) 122.30 (C-1′′) 115.64 (C-3′′, C-5′′) 106.14 (C-4′a) 98.78 (C-8′) 93.02 (C-6′) 69.53 (C-1) 69.36 (C-4) 68.88 (C-5, C-4′′′) 36.74 (C-1′′′) 21.19 (CH3–) 16.74 (C-6).
Z Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 12.81 (OH-5′; s; 1H) 7.84 (H-2′; s; 1H) 7.34 (H-2′′, H-6′′; overlapped; 2H) 6.85 (H-3′′, H-5′′; overlapped; 2H) 6.40 (H-8′; d; J5′-7′ = 2.32 Hz; 1H) 6.37 (H-6′; d; J7′-5′ = 2.3 Hz; 1H) 5.94 (H-2; ddd; J2-3 = 10.1 Hz; J2-1 = 2.7 Hz; J2-4 = −1.3 Hz) 5.85 (H-3; ddd; J3-2 = 10.1 Hz; J3-4 = 3.5 Hz; J3-1 = −1.7 Hz; 1H) 5.80/5.83 (H-2′′′; H-3′′′; overlapped; 2H) 4.91 (H-4; overlapped; 1H) 4.65 (H-4′′′; d; J4′′-3′′ = 4.6 Hz; 2H) 4.26 (H-1; overlapped; 1H) 3.96 (H-5; overlapped; 1H) 2.49 (H-1′′′a; overlapped; 1H) 2.44 (H-1′′′b; ddd; J1′′b-1′′a = 14.60 Hz; J1′′b-1 = J1′′b-2′′ = 6.0 Hz; 1H) 2.09 (OAc; s; 3H) 1.27 (H-6; t; J6-5 = 6.63 Hz × 3; 3H).
13C NMR (75 MHz, CDCl3) δ ppm: 180.87 (C-4′; overlapped) 170.07 (C=O; overlapped) 164.46 (C-7′; overlapped) 162.46 (C-5′) 157.81 (C-4′′; overlapped) 156.39 (C-8′a; overlapped) 152.77 (C-2′; overlapped) 133.09 (C-2) 130.15 (C-2′′′, C-2′′, C-6′′; overlapped) 126.16 (C-3′′′) 123.68 (C-3′) 123.23 (C-3) 122.30 (C-1′′; overlapped) 115.64 (C-3′′, C-5′′; overlapped) 106.17 (C-4′a) 98.72 (C-8′) 93.02 (C-6′; overlapped) 69.31 (C-1) 69.27 (C-4) 69.07 (C-5) 64.54 (C-4′′′) 32.43 (C-1′′′) 21.19 (CH3–; overlapped) 16.74 (C-6; overlapped).
LRMS [M + Na]
+. Experimental: 501.2; calculated: 501.2.
2.4.13. 1′,4′-Bis-C-(4-O-acetyl-2,3,6-trideoxy-α-L-erythro-heks-2-enpyranosyl)-but-2′-en (4f)
E Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 5.92 (H-2; ddd; J2-3 = 10.2 Hz; J2-1 = 2.2 Hz; J2-4 = 1.5 Hz; 2H) 5.77 (H-3; ddd; J3-2 = 10.2 Hz; J3-4 = 3.4 Hz; J3-1 = 2.2 Hz; 2H) 5.58 (H-2′; ddddd; J2′-3′ = 15.5 Hz; J2′-1′a = 6.5 Hz; J2′-1′b = 7.5 Hz; J2′-4′a = J2′-4′b = −1.5 Hz; 1H) 5.58 (H-3′; ddddd; J3′-2′ = 15.5 Hz; J3′-4′a = 6.5 Hz; J3′-4′b = 7.5 Hz; J3′-1′a = J3′-1′b = −1.5 Hz; 1H) 4.88 (H-4; dddd; J4-5 = 4.7 Hz; J4-3 = 3.4 Hz; J4-2 = 1.4 Hz; J4-1 = 2.2 Hz; 2H) 4.17 (H-1; ddddd; J1-1′a = 9.0 Hz; J1-1′b = 6.7 Hz; J1-2 = J1-3 = J1-4 = 2.2 Hz; 2H) 3.91 (H-5; dq; J5-6 = 6.6 Hz × 3; J5-4 = 4.7 Hz; 2H) 2.46/2.40 (H-1′a, H-4′a; m; 2H) 2.28 (H-1′b; dddd; J1′b-1′a = 14.0 Hz; J1′b-2′ = 7.5 Hz; J1′b-1 = 6.7 Hz; J1′b-3′ = −1.5 Hz; 1H) 2.28 (H-4′b; dddd; J4′b-4′a = 14.0 Hz; J4′b-3′ = 7.5 Hz; J4′b-1 = 6.7 Hz; J4′b-2′ = −1.5 Hz; 1H) 2.09 (CH3; s; 6H) 1.23 (H-6; d; J6-5 = 6.6; 6H).
13C NMR (150 MHz, CDCl3) δ ppm: 16.92 (C-6) 21.18 (CH3) 37.17 (C-1′, C-4′) 68.62 (C-4) 69.57 (C-5) 70.13 (C-1) 122.94 (C-3) 128.66 (C-2′, C-3′) 133.46 (C-2) 170.69 (C=O).
Z Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 5.93 (H-2; ddd; J2-3 = 10.2 Hz; J2-1 = 2.2 Hz; J2-4 = 1.4 Hz; 2H) 5.79 (H-3; ddd; J3-2 = 10.2 Hz; J3-4 = 3.5 Hz; J3-1 = 2.2 Hz; 2H) 5.61 (H-2′; ddddd; J2′-3′ = 11.0 Hz; J2′-1′a = 6.5; J2′-1′b = 7.5 Hz; J2′-4′a = J2′-4′b = −1.6 Hz; 1H) 5.61 (H-3′; ddddd; J3′-2′ = 11.0 Hz; J3′-4′a = 6.5 Hz; J3′-4′b = 7.5 Hz; J3′-1′a = J3′-1′b = −1.6 Hz; 1H) 4.88 (H-4; dddd; J4-5 = 4.9 Hz; J4-3 = 3.5 Hz; J4-2 = 1.4 Hz; J4-1 = 2.2 Hz; 2H) 4.19 (H-1; ddddd; J1-1′a = 9.0 Hz; J1-1′b = 6.7 Hz; J1-2 = J1-3 = J1-4 = 2.2 Hz; 2H) 3.92 (H-5; dq; J5-6 = 6.6 Hz × 3; J5-4 = 4.9 Hz; 2H) 2.46/2.40 (H-1′a, H-4′a; overlapped; 2H) 2.34 (H-1′b; dddd; J1′b-1′a = 15.2 Hz; J1′b-2′ = 7.5 Hz; J1′b-1 = 6.7 Hz; J1′b-3′ = −1.6 Hz; 1H) 2.34 (H-4′b; dddd; J4′b-4′a = 15.2 Hz; J4′b-3′ = 7.5 Hz; J4′b-1 = 6.7 Hz; J4′b-2′ = −1.6 Hz; 1H) 2.09 (CH3; s; 6H) 1.23 (H-6; d; J6-5 = 6.6 Hz; 6H).
13C NMR (150 MHz, CDCl3) δ ppm: 16.92 (C-6) 21.18 (CH3) 32.11 (C-1′, C-4′) 68.74 (C-4) 69.52 (C-5) 69.92 (C-1) 123.06 (C-3) 127.45 (C-2′, C-3′) 133.39 (C-2) 170.69 (C=O).
HRMS [M + Na]
+. Experimental: 387.1760; calculated: 387.1778.
2.4.14. 7′-O-(1′′′-C-(4,6-Di-O-acetyl-2,3-dideoxy-α-D-erythro-heks-2-enpyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3g)
E Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 12.81 (OH-5′; s; 1H) 7.84 (H-2′; s; 1H) 7.36 (H-2′′, H-6′′; d; J10′-11′,14′-13′ = 8.63 Hz; 2H) 6.87 (H-3′′, H-5′′; d; J11′-10,13′-14′ = 7.96 Hz; 2H) 6.39 (H-8′; d; J5′-7′ = 2.65 Hz; 1H) 6.38 (H-6′; d; J7′-5′ = 2.65 Hz; 1H) 5.96/5.79 (H-2, H-3, H-2′′′, H-3′′′; m; 4H) 5.14 (H-4; broad signal; 1H) 4.55 (H-4′′′; d; J4′′-3′′ = 5.97 Hz; 2H) 4.32 (H-1; ddd; J1-1′′a = 7.8 Hz; J1-1′′b = 5.47 Hz; J1-2 = 2.65 Hz; 1H) 4.27 (H-6a; dd; J6a-6b = 11.94 Hz; J6a-5 = 6.63 Hz; 1H) 4.16 (H-6b; dd; J6b-6a = 11.61 Hz; J6b-5 = 3.65 Hz; 1H) 3.98 (H-5; ddd; J5-6a = 6.3 Hz; J5-4 = 6.3 Hz; J5-6b = 3.98 Hz; 1H) 2.52 (H-1′′′a; ddd; J1′′a-1′′b = 13.93 Hz; J1′′a-1 = 6.97 Hz; J1′′a-2′′ = 6.97 Hz; 1H) 2.39 (H-1′′′b; ddd; J1′′a-1′′b = 14.60 Hz; J1′′b-1 = 5.97 Hz; J1′′b-2′′ = 5.97 Hz; 1H) 2.10 (OAc; s; 6H).
13C NMR (150 MHz, CDCl3) δ ppm: 180.87 (C-4′) 170.96 (C=O) 170.53 (C=O) 164.44 (C-7′) 162.57 (C-4′) 157.88 (C-4′′) 156.18 (C-8′a) 152.76 (C-2′) 132.59 (C-2) 131.07 (C-2′′′) 130.23 (C-2′′, C-6′′) 126.83 (C-3′′′) 123.90 (C-3) 123.68 (C-3′) 122.60 (C-1′′) 115.61 (C-3′′, C-5′′) 106.23 (C-4′a) 98.74 (C-6′) 93.08 (C-8′) 71.16 (C-1) 69.91 (C-5) 68.87 (C-4′′′) 64.87 (C-4) 62.77 (C-6) 36.60 (C-1′′′) 21.08 (CH3–) 20.83 (CH3–).
Z Isomer. 1H NMR (600 MHz, CDCl3) δ ppm: 12.82 (OH-5′; s; 1H) 7.85 (H-2′; s; 1H) 7.36 (H-2′′, H-6′′) 6.87 (H-3′′, H-5′′; 2H; overlapped) 6.41 (H-8′; d; J5′-7′ = 2.65 Hz; 1H) 6.37 (H-6′; d; J7′-5′ = 2.65 Hz; 1H) 5.96–5.79 (H-2, H-3, H-2′′′, H-3′′′; m; 4H; overlapped) 5.14 (H-4; broad signal; 1H; overlapped) 4.66 (H-4′′′; d; J4′′-3′′ = 5.31 Hz; 2H) 4.32 (H-1; 1H; overlapped) 4.29 (H-6a; d; J6a-6b = 11.94 Hz; 1H; partially overlapped) 4.16 (H-6b; 1H; overlapped) 4.01 (H-5; ddd; J5-6a = 6.47 Hz; J5-4 = 6.47 Hz; J5-6b = 3.65 Hz; 1H) 2.52 (H-1′′′a; 1H; overlapped) 2.46 (H-1′′′b; ddd; J1′′b-1′′a = 14.60 Hz; J1′′b-1 = 5.97 Hz; J1′′b-2′′ = 5.97 Hz; 1H) 2.10 (OAc; s; 6H).
13C NMR (150 MHz, CDCl3) δ ppm: 180.87 (C-4′; overlapped) 170.96 (C=O; overlapped) 170.53 (C=O; overlapped) 164.44 (C-7′; overlapped) 162.57 (C-5′; overlapped) 157.88 (C-4′′; overlapped) 156.18 (C-8′a; overlapped) 152.76 (C-2′; overlapped) 132.50 (C-2) 130.23 (C-2′′, C-6′′; overlapped) 129.88 (C-2′′′) 126.30 (C-3′′′) 124.02 (C-3) 123.68 (C-3′; overlapped) 122.60 (C-4′a; overlapped) 115.61 (C-3′′, C-5′′; overlapped) 106.23 (C-3′; overlapped) 98.68 (C-6′) 93.11 (C-8′) 70.93 (C-1) 70.15 (C-5) 64.55 (C-4′′′) 64.87 (C-4; overlapped) 62.77 (C-6; overlapped) 32.11 (C-1′′′) 21.08 (CH3; overlapped) 20.83 (CH3; overlapped).
HRMS [M + Na]
+. Experimental: 559.1560; calculated: 559.1575.
2.4.15. 1′,4′-Bis-C-(4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-heks-2-enpyranosyl)-but-2′-en (4g)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.93 (H-2; ddd; J2-3 = 10.45 Hz; J2-1 = 2.41 Hz; J2-4 = 1.51 Hz; 2H) 5.80 (H-3; ddd; J3-2 = 10.30 Hz; J3-4 = 2.83 Hz; J2-1 = 2.08 Hz; 2H) 5.58 (H-2′, H-3′; t; 3.7 Hz × 2; 2H) 5.14 (H-4; m; 2H) 4.26 (H-6a; dd; J6a-6b = 11.92 Hz; J6a-5 = 6.32 Hz; 2H) 4.26 (H-1; overlapped przez H-6a; 2H) 4.14 (H-6b; ddd; J6b-6a = 12.06 Hz; J6b-5 = 3.59 Hz; 2H) 3.95 (H-5; ddd; J5-6a = 6.43 Hz; J5-4 = 6.43; J5-6b = 3.38 Hz; 2H) 2.49/2.25 (H-1′a, H-1′b, H-4′a, H-4′b; m; 4H) 2.10 (–CH3; s; 12H).
13C NMR (75 MHz, CDCl3) δ ppm: 170.83 (C=O) 170.42 (C=O) 132.85 (C-2) 128.61 (C-2′, C-3′) 123.65 (C-3) 71.64 (C-5) 69.83 (C-1) 64.92 (C-4) 62.79 (C-6) 36.77 (C-1′, C-4′) 21.10 (CH3) 20.85 (CH3).
Z Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 5.94 (H-2; ddd; J2-3 = 10.45 Hz; J2-1 = 2.41 Hz; J2-4 = 1.36 Hz; 2H) 5.82 (H-3; ddd; J3-2 = 10.30 Hz; J3-4 = 2.84 Hz; J2-1 = 2.08 Hz; 2H) 5.61 (H-2′, H-3′; t; 4.9 Hz × 2; 2H) 5.14 (H-4; m; 2H) 4.26 (H-6a; overlapped; 2H) 4.26 (H-1; overlapped; 2H) 4.14 (H-6b; overlapped; 2H) 3.96 (H-5; ddd; J5-6a = 6.57 Hz; J5-4 = 6.57 Hz; J5-6b = 3.23 Hz; 2H) 2.49–2.25 (H-1′a, H-1′b, H-4′a, H-4′b; m; 4H) 2.09 (–CH3; s; 12H).
13C NMR (75 MHz, CDCl3) δ ppm: 170.83 (C=O; overlapped) 170.42 (C=O; overlapped) 132.77 (C-2) 127.30 (C-2′, C-3′) 123.77 (C-3) 71.39 (C-5) 69.98 (C-1) 64.92 (C-4; overlapped) 62.79 (C-6; overlapped) 31.71 (C-1′, C-4′) 21.10-20.85 (CH3; overlapped).
HRMS [M + Na]
+. Experimental: 503.1906; calculated: 503.1888.
2.4.16. 7′-O-(1′′′-C-(4,6-Di-O-acetyl-2,3-dideoxy-α-D-treo-heks-2-enpyranosyl)-but-2′′′-en-4′′′-yl)-genistein (3h)
Isomer E. 1H NMR (300 MHz, CDCl3) δ ppm: 12.81 (H-5′; s; 1H) 7.83 (H-2′; s; 1H) 7.35/7.33 (H-2′′, H-6′′; m; 2H) 6.87/6.84 (H-3′′; H-5′′; m; 2H) 6.39 (H-8′; d; J5′-7′ = 2.3 Hz; 1H) 6.35 (H-6′; d; J7′-5′ = 2.3 Hz; 1H) 6.07–5.98 (H-2, H-3; m; 2H) 5.91 (H-2′′′; ddd; J2′′-3′′ = 15.6 Hz; J2′′-1′′a = 6.5 Hz; J2′′-1′′b = 6.4 Hz; 1H) 5.80 (H-3′′′; dt; J3′′-2′′ = 15.6 Hz; J3′′-4′′ = 5.3 Hz × 2; 1H) 5.09 (H-4; dd; J4-3 = 4.3 Hz; J4-5 = 2.7 Hz; 1H) 4.54 (H-4′′′; d; J4′′-3′′ = 5.3 Hz; 1H) 4.42–4.37 (H-1; m; 1H) 4.24/4.21 (H-6a, Hz; J1′′a-1 = 8.3 Hz; 1H) 2.35 (H-1′′′b; ddd; J1′′b-1′′a = 14.6 Hz; J1′′b-2′′ = 6.4 Hz; J1′′b-1 = 5.7 Hz; 1H) 2.09 (–CH3; s; 3H) 2.09 (–CH3; s; 3H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.79 (–CH3) 20.87 (–CH3) 35.22 (C-1′′′) 62.89 (C-6) 63.80 (C-4) 68.07 (C-5) 68.80 (C-4′′′) 72.11 (C-1) 93.03 (C-8′) 98.74 (C-6′) 106.19 (C-4′a) 115.62 (C-3′′, C-5′′) 122.27 (C-3) 122.49 (C-1′′) 123.67 (C-3′) 126.94 (C-3′′′) 130.18 (C-2′′, C-6′′) 130.84 (C-2′′′) 134.37 (C-2) 152.79 (C-2′) 156.34 (C-5′) 157.82 (C-8′a) 162.47 (C-4′′) 164.42 (C-7′) 170.70 (C=O) 170.98 (C=O) 180.88 (C-4′).
Z Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 12.81 (H-5′; s; 1H) 7.85 (H-2′; s; 1H) 7.35/7.33 (H-2′′, H-6′′; overlapped; 2H) 6.87/6.84 (H-3′′; H-5′′; overlapped; 2H) 6.40 (H-8′; d; J5′-7′ = 2.3 Hz; 1H) 6.36 (H-6′; d; J7′-5′ = 2.3 Hz; 1H) 6.07/5.98 (H-2, H-3; overlapped; 2H) 5.85/5.76 (H-2′′′, H-3′′′; overlapped; 1H) 5.12 (H-4; dd; J4-3 = 4.0 Hz; J4-5 = 2.2 Hz; 1H) 4.65 (H-4′′′; d; J4′′-3′′ = 4.6 Hz; 1H) 4.42/4.37 (H-1; overlapped; 1H) 4.24/4.21 (H-6a, H-6b; overlapped; 2H) 4.18/4.13 (H-5; overlapped; 1H) 2.57/2.43 (H-1′′′a, H-1′′′b; overlapped; 2H) 2.10 (–CH3; s; 3H) 2.08 (–CH3; s; 3H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.79 (–CH3, overlapped) 20.87 (–CH3, overlapped) 31.04 (C-1′′′) 62.81 (C-6) 63.80 (C-4) 64.43 (C-4′′′) 68.18 (C-5, overlapped) 71.92 (C-1) 93.03 (C-8′, overlapped) 98.68 (C-6′) 106.24 (C-4′a) 115.62 (C-3′′, C-5′′, overlapped) 122.39 (C-3) 122.49 (C-1′′, overlapped) 123.67 (C-3′, overlapped) 126.24 (C-3′′′) 129.87 (C-2′′′) 130.18 (C-2′′, C-6′′, overlapped) 134.16 (C-2) 152.79 (C-2′, overlapped) 156.34 (C-5′, overlapped) 157.82 (C-8′a, overlapped) 162.517 (C-4′′) 164.39 (C-6′) 170.70 (C=O, overlapped) 170.98 (C=O, overlapped) 180.88 (C-4′, overlapped).
HRMS [M + Na]
+. Experimental: 559.1552; calculated: 559.1575.
2.4.17. 1′,4′-Bis-C-(4,6-di-O-acetyl-2,3-dideoxy-α-D-treo-heks-2-enpyranosyl)-but-2′-en (4h)
E Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 6.04 (H-2 dd; J2-3 = 10.2 Hz; J2-1 = 2.7 Hz; 2H) 5.98 (H-3; ddd; J3-2 = 10.2 Hz; J3-4 = 4.7 Hz; J3-1 = 1.7 Hz; 2H) 5.59 (H-2′, H-3′; t; 3.8 Hz × 2; 2H) 5.08 (H-4; dd; J4-3 = 4.7 Hz; J4-5 = 2.3 Hz; 2H) 4.32 (H-1; dddd; J1-1′a = 7.8; J1-1′b = 5.2 Hz; J1-2 = 2.7 Hz; J1-3 = 1.7 Hz; 2H) 4.21/4.19 (H-6a, H-6b; m; 4H) 4.16–4.10 (H-5; m; 2H) 2.46–2.35 (H-1′a, H-4′a; m; 2H) 2.31/2.23 (H-1′b, H-4′b; m; 2H) 2.09 (–CH3; s; 6H) 2.08 (–CH3; s; 6H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.81 (–CH3) 20.90 (–CH3) 35.72 (C-1′, C-4′) 62.86 (C-6) 63.77 (C-4) 68.04 (C-5) 72.58 (C-1) 122.04 (C-3) 128.53 (C-2′, C-3′) 134.69 (C-2) 170.52 (C=O) 170.70 (C=O).
Z Isomer. 1H NMR (300 MHz, CDCl3) δ ppm: 6.06 (H-2; dd; J2-3 = 10.4 Hz; J2-1 = 2.9 Hz; 2H) 5.98 (H-3; overlapped; 2H) 5.63 (H-2′; t; 4.8 Hz × 2; 2H) 5.08 (H-4; overlapped; 2H) 4.32 (H-1; overlapped; 2H) 4.21/4.19 (H-6a, H-6b; overlapped; 4H) 4.16/4.10 (H-5; overlapped; 2H) 2.46/2.35 (H-1′a, H-1′b, H-4′a, H-4′b; overlapped; 4H) 2.09/2.08 (–CH3; overlapped; 12H).
13C NMR (75 MHz, CDCl3) δ ppm: 20.81 (–CH3, overlapped) 20.90 (–CH3, overlapped) 30.66 (C-1′, C-4′) 62.86 (C-6, overlapped) 63.74 (C-4) 68.09 (C-5) 72.32 (C-1) 122.16 (C-3) 127.23 (C-2′, C-3′) 134.59 (C-2) 170.52 (C=O, overlapped) 170.70 (C=O, overlapped).
HRMS [M + Na]
+. Experimental: 503.1911; calculated: 503.1888.