3.2. General Procedures for the Preparation of 1-Substituted 1,2,3-Triazole-Mollugin Derivatives
To a solution of 0.2 mmol of the corresponding azide in 3 mL mixed solution (
t-BuOH/H
2O = 1:1,
v/v) was added
O-propargylated mollugin (0.2 mmol), sodium ascorbate (0.02 mmol), CuSO
4·5H
2O (0.02 mmol). The reaction mixture was stirred for 48 h at room temperature before it was quenched by saturated NH
4Cl aqueous solution (4 mL), and the mixture was extracted with ethyl acetate (3 × 6 mL). The combined organic layer was washed with brine (2 × 15 mL), and dried over Na
2SO
4, and filtered [
31,
32]. After removal of the solvent under vacuum, the residue was purified by flash column chromatography on silica gel (10/1 to 2/1 petroleum ether/EtOAc) provided compound
5–44.
1-O-((1-(4-methoxyphenyl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (5). Yield: 89%, yellow oil, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.3, 3.3 Hz), 8.17 (dd, 1H, J = 6.3, 3.3 Hz), 8.01 (s, 1H), 7.64 (d, 2H, J = 8.9 Hz), 7.52 (m, 2H), 7.02 (d, 2H, J = 8.9 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.32 (s, 2H), 3.94 (s, 3H), 3.86 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 159.9, 145.9, 145.4, 144.7, 130.5, 130.3, 127.9, 127.2, 127.1, 126.8, 122.8, 122.5, 122.4, 76.6, 69.1, 55.7, 52.5, 27.7; ESIMS: m/z 494 [M+Na]+, HRESIMS: calcd for C27H25N3O5Na [M+Na]+ 494.1688, found 494.1686.
1-O-((1-(4-methoxy-2-methylphenyl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (6). Yield: 70%, yellow solid, MP: 157–159 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.4, 3.3 Hz), 8.15 (dd, 1H, J = 6.5, 3.2 Hz), 7.72 (s, 1H), 7.51 (m, 2H), 7.23 (d, 1H, J = 8.5 Hz), 6.84 (s, 1H), 6.82 (d, 1H, J = 8.5 Hz), 6.44 (d, 1H, J = 10.0 Hz), 5.85 (d, 1H, J = 10.0 Hz), 5.34 (s, 2H), 3.95 (s, 3H), 3.84 (s, 3H), 2.12 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 160.4, 145.7, 145.3, 143.6, 135.4, 130.3, 129.6, 128.1, 127.3, 127.1, 127.0, 126.7, 125.3, 122.9, 122.4, 121.2, 119.9, 116.3, 112.4, 111.8, 76.6, 68.9, 55.6, 52.5, 27.7, 18.0; ESIMS: m/z 508 [M+Na]+, HRESIMS: calcd for C28H27N3O5Na [M+Na]+ 508.1840, found 508.1843.
1-(3-chloro-4-methoxyphenyl)-4-ethyl-1H-1,2,3-triazole-O-mollugin (7). Yield: 72%, yellow solid, MP: 125–127 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.4, 3.3 Hz), 8.14 (dd, 1H, J = 6.4, 3.3 Hz), 8.00 (s, 1H), 7.78 (d, 1H, J = 2.6 Hz), 7.60 (dd, 1H, J = 8.9, 2.6 Hz), 7.52 (m, 2H), 7.03 (d, 1H, J = 8.9 Hz), 6.44 (d, 1H, J = 10.0 Hz), 5.70 (d, 1H, J = 10.0 Hz), 5.31 (s, 2H), 3.96 (s, 3H), 3.94 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 155.4, 145.7, 145.4, 144.9, 130.5, 130.3, 127.9, 127.2, 127.1, 126.8, 123.6, 123.1, 122.7, 122.5, 121.7, 121.1, 119.8, 112.4, 76.6, 69.0, 56.5, 52.5, 27.7; ESIMS: m/z 528 [M+Na]+, HRESIMS: calcd for C27H23N3O5ClNa [M+Na]+ 528.1296, found 528.1297.
1-O-((1-(3-fluoro-4-methoxyphenyl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (8). Yield: 78%, yellow oil, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.5, 3.3 Hz), 8.14 (dd, 1H, J = 6.5, 3.2 Hz), 8.01 (s, 1H), 7.52 (m, 3H), 7.44 (m, 1H), 7.07 (t, 1H, J = 8.8 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.32 (s, 2H), 3.95 (s, 3H), 3.94 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 153.6, 151.1, 148.2, 145.7, 145.5, 144.9, 130.3, 127.9, 127.2, 127.1, 126.8, 122.7, 122.5, 121.7, 121.1, 119.8, 116.6, 113.8, 112.4, 109.9, 76.6, 69.0, 56.5, 52.5, 27.7; ESIMS: m/z 512 [M+Na]+, HRESIMS: calcd for C27H24N3O5FNa [M+Na]+ 512.1594, found 512.1592.
1-O-((1-(5-fluoro-2-methoxyphenyl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (9). Yield: 48%, yellow oil, 1H NMR (CDCl3, 400 MHz) δ 8.26 (s, 1H), 8.22 (dd, 1H, J = 6.4, 3.3 Hz), 8.17 (dd, 1H, J = 6.4, 3.3 Hz), 7.65 (dd, 1H, J = 8.7, 3.1 Hz), 7.52 (m, 2H), 7.13 (m, 1H), 7.03 (m, 1H), 6.44 (d, 1H, J = 9.9 Hz), 5.69 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.95 (s, 3H), 3.88 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 157.8, 155.4, 147.1, 145.9, 145.4, 143.8, 130.3, 128.0, 127.1, 127.0, 126.8, 125.3, 122.9, 122.5, 121.1, 119.8, 116.2, 113.3, 112.7, 112.5, 76.6, 69.0, 56.6, 52.5, 27.7; ESIMS: m/z 512 [M+Na]+, HRESIMS: calcd for C27H24N3O5FNa [M+Na]+ 512.1590, found 512.1592.
1-O-((1-(5-chloro-2-methoxyphenyl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (10). Yield: 92%, yellow solid, MP: 159–161 °C, 1H NMR (CDCl3, 400 MHz) δ 8.24–8.20 (m, 2H), 8.17 (dd, 1H, J = 6.3, 3.4 Hz), 7.86 (d, 1H, J = 2.6 Hz), 7.52 (m, 2H), 7.38 (dd, 1H, J = 8.9 Hz, 2.6 Hz), 7.01 (d, 1H, J = 8.9Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9Hz), 5.33 (s, 2H), 3.95 (s, 3H), 3.89 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 149.6, 145.9, 145.4, 143.8, 130.3, 129.7, 128.0, 127.1, 127.0, 126.9, 126.8, 126.3, 125.3, 122.9, 122.5, 121.1, 119.8, 113.4, 112.4, 76.6, 69.1, 56.4, 52.5, 27.7; ESIMS: m/z 528 [M+Na]+, HRESIMS: calcd for C27H24N3O5ClNa [M+Na]+ 528.1296, found 528.1297.
1-O-((1-(3,5-dimethoxyphenyl) -1H-1,2,3-triazol)-4-yl)methyl)-mollugin(11). Yield: 84%, yellow solid, MP: 51–53 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.4, 3.5 Hz), 8.16 (dd, 1H, J = 6.4, 3.5 Hz), 8.07 (s, 1H), 7.52 (m, 2H), 6.91 (d, 2H, J = 2.2 Hz), 6.51 (t, 1H, J = 2.3 Hz), 6.44 (d, 1H, J = 9.9Hz), 5.69 (d, 1H, J = 9.9 Hz), 5.32 (s, 2H), 3.94 (s, 3H), 3.85 (s, 6H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 161.5, 145.8, 145.4, 144.8, 138.5, 130.3, 127.9, 127.2, 127.1, 126.8, 122.7, 122.5, 121.7, 121.1, 119.9, 112.4, 100.7, 99.1, 76.6, 69.1, 55.7, 52.5, 27.7; ESIMS: m/z 524 [M+Na]+, HRESIMS: calcd for C28H27N3O6Na [M+Na]+ 524.1793, found 524.1792.
1-O-((1-(benzo[d][1,3]dioxol-5-yl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (12). Yield: 72%, yellow solid, MP: 73–75 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.5, 3.3 Hz), 8.15 (dd, 1H, J = 6.5, 3.3 Hz), 7.98 (s, 1H), 7.52 (m, 2H), 7.24 (d, 1H, J = 2.2 Hz), 7.14 (dd, 1H, J = 8.3, 2.2 Hz), 6.90 (d, 1H, J = 8.3 Hz), 6.44 (d, 1H, J = 9.9 Hz), 6.06 (s, 2H), 5.69 (d, 1H, J = 9.9 Hz), 5.31 (s, 2H), 3.94 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 148.6, 148.1, 145.8, 145.4, 144.7, 131.5, 130.3, 127.9, 127.1, 127.1, 126.8, 122.8, 122.5, 121.9, 121.1, 119.9, 114.5, 112.4, 108.5, 103.0, 102.1, 76.6, 69.0, 52.5, 27.7; ESIMS: m/z 508 [M+Na]+, HRESIMS: calcd for C27H23N3O6Na [M+Na]+ 508.1474, found 508.1479.
1-O-((1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (13). Yield: 82%, yellow solid, MP: 71–73 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.4, 3.3 Hz), 8.16 (dd, 1H, J = 6.4, 3.2 Hz), 7.98 (s, 1H), 7.52 (m, 2H), 7.27 (d, 1H, J = 2.6 Hz), 7.17 (dd, 1H, J = 8.7, 2.6 Hz), 6.96 (d, 1H, J = 8.7Hz) 6.42 (d, 1H, J = 9.9Hz), 5.68 (d, 1H, J = 9.9 Hz), 4.29 (s, 4H), 3.92 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.8, 145.3, 144.6, 144.1, 130.9, 130.3, 127.9, 127.1, 127.0, 126.8, 122.8, 122.5, 121.7, 121.1, 119.9, 118.1, 114.0, 112.4, 110.5, 76.6, 69.1, 64.4, 52.5, 27.7; ESIMS: m/z 522 [M+Na]+, HRESIMS: calcd for C28H25N3O6Na [M+Na]+ 522.1638, found 522.1636.
1-O-((1-(3,4,5-trimethoxyphenyl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin(14). Yield: 76%, yellow solid, MP: 55–57 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.5, 3.3 Hz), 8.14 (dd, 1H, J = 6.4, 3.2 Hz), 8.03 (s, 1H), 7.52 (m, 2H), 6.95 (s, 2H) 6.44 (d, 1H, J = 9.9Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.93 (s, 9H), 3.89 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 153.9, 145.7, 145.5, 144.8, 138.4, 132.9, 130.3, 127.9, 127.2, 127.1, 126.8, 122.7, 122.5, 121.8, 121.3, 119.8, 112.4, 98.7, 76.6, 69.1, 61.1, 56.5, 52.5, 27.7; ESIMS: m/z 554 [M+Na]+, HRESIMS: calcd for C29H29N3O7Na [M+Na]+ 554.1899, found 554.1898.
1-O-((1-(2,3,4-trimethoxyphenyl)-1H-1,2,3-triazol)-4-yl)methyl)-mollugin (15). Yield: 47%, yellow solid, MP: 123–125 °C, 1H NMR (CDCl3, 400 MHz) δ 8.25–8.15 (m, 2H), 8.07 (s, 1H), 7.52 (m, 2H), 7.42 (d, 2H, 9.0 Hz), 6.79 (d, 1H, 9.0 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.69 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.97 (s, 3H), 3.93 (s, 3H), 3.93 (s, 3H), 3.73 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 154.4, 146.7, 145.9, 145.3, 143.7, 142.7, 130.2, 128.1, 127.1, 127.0, 126.8, 125.2, 124.5, 122.9, 122.4, 121.1, 120.1, 119.9, 112.4, 107.2, 76.5, 69.0, 61.6, 61.2, 56.2, 52.5, 27.7; ESIMS: m/z 554 [M+Na]+, HRESIMS: calcd for C29H29N3O7Na [M+Na]+ 554.1898, found 554.1898.
1-O-((1-(2-hydroxyphenyl)-1H-1,2,3-triazol-4-yl)methyl)-O-mollugin (16). Yield: 67%, white solid, MP: 183–185 °C, 1H NMR (CDCl3, 400 MHz) δ 9.59 (s, 1H), 8.24 (dd, 1H, J = 6.5, 3.1 Hz), 8.14 (m, 2H), 7.54 (m, 2H), 7.42 (dd, 1H, J = 8.1, 1.6 Hz), 7.32 (t, 1H, J = 7.1 Hz), 7.20 (dd, 1H, J = 8.3, 1.4 Hz), 6.42 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.35 (s, 2H), 3.93 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 149.5, 145.6, 145.5, 144.2, 130.4, 130.0, 127.7, 127.2, 127.1, 126.9, 123.0, 122.6, 122.5, 121.9, 121.2, 120.4, 120.4, 119.8, 119.4, 112.3, 76.6, 68.6, 52.7, 27.7; ESIMS: m/z 456 [M−H]−, HRESIMS: calcd for C26H23N3O5Na [M−H]− 456.1569, found 456.1565.
1-O-((1-(3-hydroxyphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (17). Yield: 55%, white solid, MP: 182–184 °C, 1H NMR (CDCl3, 400 MHz) δ 9.44 (s, 1H), 8.45 (s, 1H), 8.24–8.13 (m, 3H), 7.54 (m, 2H), 7.36 (t, 1H, J = 8.1 Hz), 7.07 (dd, 1H, J = 7.9, 2.0 Hz), 7.01 (dd, 1H, J = 8.3, 2.4 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.35 (s, 2H), 3.95 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 158.6, 145.7, 145.5, 144.6, 137.5, 130.6, 130.3, 127.8, 127.3, 127.1, 126.8, 122.6, 122.6, 121.6, 121.1, 119.8, 116.9, 112.4, 110.0, 109.0, 76.6, 68.6, 52.6, 27.7; ESIMS: m/z 456 [M−H]−, HRESIMS: calcd for C26H23N3O5Na [M−H]− 456.1569, found 456.1565.
1-O-((1-(4-hydroxyphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (18). Yield: 51%, yellow solid, MP: 209–211 °C, 1H NMR ((CD3)2CO, 400 MHz) δ 8.90 (s, 1H), 8.53 (s, 1H), 8.27 (m, 1H), 8.21 (m, 1H), 7.73 (d, 2H, J = 8.8 Hz), 7.60 (m, 2H), 7.05 (d, 2H, J = 8.8 Hz), 6.46 (d, 1H, J = 9.9 Hz), 5.85 (d, 1H, J = 9.9 Hz), 5.27 (s, 2H), 3.97 (s, 3H), 1.53 (s, 6H); 13C NMR ((CD3)2CO, 100 MHz) δ 167.0, 157.8, 145.6, 144.9, 144.1, 130.7, 129.9, 128.0, 127.1, 127.0, 126.5, 122.9, 122.3, 122.3, 122.2, 121.8, 119.5, 116.1, 112.4, 76.6, 68.7, 51.9, 26.9; ESIMS: m/z 456 [M−H]−, HRESIMS: calcd for C26H23N3O5Na [M−H]− 456.1567, found 456.1565.
1-O-((1-(3-chloro-4-hydroxyphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (19). Yield: 42%, white solid, MP: 196–198 °C, 1H NMR ((CD3)2CO, 400 MHz) δ 9.41(s,1H), 8.63 (s, 1H), 8.26 (m, 1H), 8.22 (m, 1H), 7.93 (d, 1H, J = 2.7 Hz), 7.75 (dd, 1H, J = 8.8, 2.7 Hz), 7.60 (m, 2H), 7.24 (d, 1H, J = 8.8 Hz), 6.46 (d, 1H, J = 9.9 Hz), 5.86 (d, 1H, J = 9.9 Hz), 5.27 (s, 2H), 3.96 (s, 3H), 1.53 (s, 6H); 13C NMR ((CD3)2CO, 100 MHz) δ 167.0, 153.4, 145.5, 144.9, 144.3, 130.7, 130.3, 128.0, 127.1, 127.1, 126.5, 122.8, 122.5, 122.4, 122.2, 121.9, 120.9, 120.7, 119.5, 117.3, 112.4, 76.6, 68.6, 51.9, 26.9; ESIMS: m/z 490 [M−H]−, HRESIMS: calcd for C26H22N3O5ClNa [M−H]− 490.1174, found 490.1175.
1-O-((1-(3-(hydroxymethyl)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (20). Yield: 40%, yellow solid, MP: 151–153 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.6, 3.1 Hz), 8.14 (dd, 1H, J = 6.5, 3.1 Hz), 8.10 (s, 1H), 7.76 (s, 1H)), 7.62 (dt, 1H, J = 8.0, 1.5 Hz), 7.51 (m, 2H), 7.46 (t, 1H, J = 7.8 Hz), 7.40 (d, 1H, J = 7.7 Hz), 6.43 (d, 1H, J = 9.9 Hz), 5.69 (d, 1H, J = 9.9 Hz), 5.30 (s, 2H), 4.78 (s, 2H), 3.93 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.8, 145.4, 144.8, 143.4, 137.1, 130.3, 129.8, 127.9, 127.2, 127.1, 127.0, 126.8, 122.7, 122.5, 121.6, 121.1, 119.8, 119.6, 118.9, 112.4, 76.6, 69.0, 64.3, 52.5, 27.7; ESIMS: m/z 494 [M+Na]+, HRESIMS: calcd for C27H25N3O5Na [M+Na]+ 494.1686, found 494.1686.
1-O-((1-(4-(hydroxymethyl)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (21). Yield: 40%, yellow solid, MP: 194–196 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.2, 3.3 Hz), 8.15 (dd, 1H, J = 6.1, 3.3 Hz), 8.08 (s, 1H), 7.71 (d, 2H, J = 8.0 Hz), 7.52 (m, 4H), 6.43 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.32 (s, 2H), 4.77 (s, 2H), 3.94 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.8, 145.4, 144.9, 141.9, 136.2, 130.3, 128.1, 127.9, 127.2, 127.1, 126.8, 122.7, 122.5, 121.5, 121.1, 120.8, 119.8, 112.4, 76.6, 69.1, 64.4, 52.5, 27.7; ESIMS: m/z 494 [M+Na]+, HRESIMS: calcd for C27H25N3O5Na [M+Na]+ 494.1684, found 494.1686.
1-O-((1-(2-ethylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin(22). Yield: 45%, yellow solid, MP: 73–75 °C, 1H NMR (CDCl3, 400 MHz) δ 8.21 (dd, 1H, J = 6.5, 3.3 Hz), 8.17 (dd, 1H, J = 6.4, 3.2 Hz), 7.76 (s, 1H), 7.52 (m, 2H), 7.47 (td, 1H, J = 7.4, 1.6 Hz), 7.47 (d, 1H, J = 7.4 Hz), 7.34 (td, 1H, J = 7.4, 1.6 Hz), 7.47 (dd, 1H, J = 8.0, 1.6 Hz), 6.44 (d, 1H, J = 9.9Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.36 (s, 2H), 3.96 (s, 3H), 2.46 (q, 2H, J = 7.6 Hz), 1.52 (s, 6H), 1.12 (t, 3H, J = 7.5 Hz); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.7, 145.4, 143.7, 140.0, 135.9, 130.3, 130.2, 129.8, 128.1, 127.1, 127.0, 126.7, 126.4, 125.3, 122.4, 121.1, 119.9, 112.4, 76.6, 68.9, 52.5, 27.7, 24.1, 15.0; ESIMS: m/z 492 [M+Na]+, HRESIMS: calcd for C28H27N3O4Na [M+Na]+ 492.1893, found 492.1894.
1-O-((1-(4-ethylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (23). Yield: 65%, yellow solid, MP: 70–71 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.4, 3.3 Hz), 8.17 (dd, 1H, J = 6.4, 3.3 Hz), 8.06 (s, 1H), 7.65 (d, 2H, J = 8.0 Hz), 7.53 (m, 2H), 7.35 (d, 2H, J = 8.0 Hz), 6.45 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.95 (s, 3H), 2.72 (q, 2H, J = 7.6 Hz), 1.53 (s, 6H), 1.28 (t, 3H, J = 7.8 Hz); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.9, 145.4, 145.3, 144.7, 134.9, 130.3, 129.1, 127.9, 127.2, 127.1, 126.8, 122.8, 122.5, 121.6, 121.1, 120.8, 119.9, 112.4, 76.6, 69.1, 52.5, 28.5, 27.7, 15.5; ESIMS: m/z 492 [M+Na]+, HRESIMS: calcd for C28H27N3O4Na [M+Na]+ 492.1896, found 492.1894.
1-O-((1-(4-vinylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (24). Yield: 45%, yellow solid, MP: 67–69 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.3, 3.3 Hz), 8.17 (dd, 1H, J = 6.3, 3.3 Hz), 8.07 (s, 1H), 7.72 (d, 2H, 8.3 Hz), 7.56 (d, 2H, 8.6 Hz), 8.53 (m, 2H), 6.76 (dd, 1H, J = 17.6, 10.9 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.83 (d, 1H, J = 17.6 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.36 (d, 1H, J = 10.9 Hz), 5.34 (s, 2H), 3.95 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.8, 145.4, 145.0, 138.2, 136.3, 135.5, 130.3, 127.9, 127.5, 127.2, 127.1, 126.8, 122.8, 122.5, 121.4, 121.1, 120.7, 119.9, 115.6, 112.4, 76.6, 69.1, 52.5, 27.7; ESIMS: m/z 490 [M+Na]+, HRESIMS: calcd for C28H25N3O4Na [M+Na]+ 490.1737, found 490.1737.
1-O-((1-(3-(methylthio)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (25). Yield: 82%, yellow solid, MP: 87–89 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.2, 3.5 Hz), 8.16 (dd, 1H, J = 6.6, 3.1 Hz), 8.09 (s, 1H), 7.64 (t, 1H, J = 1.9 Hz), 7.53 (m, 2H), 7.44 (m, 1H), 7.40 (d, 1H, J = 7.9 Hz), 7.30 (d, 1H, J = 7.9 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.94(s, 3H), 2.55 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.8, 145.4, 145.0, 141.4, 137.5, 130.3, 129.9, 127.9, 127.2, 127.1, 126.8, 126.4, 122.7, 122.5, 121.6, 121.1, 119.9, 118.0, 116.9, 112.4, 76.6, 69.0, 52.6, 27.7, 15.5; ESIMS: m/z 510 [M+Na]+, HRESIMS: calcd for C27H25N3O4SNa [M+Na]+ 510.1454, found 510.1458.
1-O-((1-(dibenzo[b,d]thiophen-4-yl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (26). Yield: 40%, yellow solid, MP: 149–151 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (s, 1H), 8.26–8.20 (m, 4H), 7.95 (m, 1H), 7.71 (d, 1H, J = 7.7 Hz), 7.62 (d, 1H, J = 7.7 Hz), 7.57–7.50 (m, 4H), 6.46 (d, 1H, J = 9.9 Hz), 5.71 (d, 1H, J = 9.9 Hz), 5.41 (s, 2H), 3.98 (s, 3H), 1.54 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.8, 145.5, 144.8, 140.2, 138.4, 134.8, 132.4, 132.2, 130.3, 128.0, 127.7, 127.2, 127.1, 126.8, 125.2, 124.9, 122.8, 122.8, 122.5, 122.4, 121.9, 121.8, 121.2, 119.9, 119.5, 112.4, 76.6, 69.0, 52.6, 27.7; ESIMS: m/z 570 [M+Na]+, HRESIMS: calcd for C32H25N3O4SNa [M+Na]+ 570.1457, found 570.1458.
1-O-((1-(4-isopropylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (27). Yield: 87%, yellow solid, MP: 97–99 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.3, 3.3 Hz), 8.17 (dd, 1H, J = 6.3, 3.4 Hz), 8.06 (s, 1H), 7.65 (d, 2H, J = 8.4 Hz), 7.53 (m, 2H), 7.38 (d, 2H, J = 8.3 Hz), 6.44 (d, 1H, J = 9.9Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.94 (s, 3H), 2.99 (hept, 1H, J = 7.0 Hz), 1.53 (s, 6H), 1.30 (s, 3H), 1.29 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 149.9, 145.9, 145.4, 144.7, 135.0, 130.3, 127.7, 127.2, 127.1, 126.8, 122.8, 122.5, 121.6, 121.1, 120.8, 119.9, 112.4, 76.6, 69.1, 52.5, 33.9, 27.7, 23.9; ESIMS: m/z 506 [M+Na]+, HRESIMS: calcd for C29H29N3O4Na [M+Na]+ 506.2052, found 506.2050.
1-O-((1-(3-isopropylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (28). Yield: 60%, yellow solid, MP: 55–57 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.3, 3.3 Hz), 8.17 (dd, 1H, J = 6.3, 3.3 Hz), 8.09 (s, 1H), 7.63 (s, 1H), 7.57–7.47 (m, 3H), 7.44 (t, 1H, J = 7.8 Hz), 7.32 (d, 1H, J = 7.7 Hz), 6.45 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.34 (s, 2H), 3.95 (s, 3H), 1.53 (s, 6H), 1.32 (s, 3H), 1.30 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 151.0, 145.9, 145.4, 144.8, 137.1, 130.3, 129.7, 128.0, 127.1, 127.1, 127.0, 126.8, 122.8, 122.5, 121.7, 121.1, 119.9, 119.1, 118.2, 112.4, 76.6, 69.2, 52.5, 34.2, 27.7, 23.9; ESIMS: m/z 506 [M+Na]+, HRESIMS: calcd for C29H29N3O4Na [M+Na]+ 506.2050, found 506.2050.
1-O-((1-(3-(dimethylamino)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (29). Yield: 60%, yellow solid, MP: 66–68 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.3, 3.3 Hz), 8.17 (dd, 1H, J = 6.3, 3.3 Hz), 8.07 (s, 1H), 7.53 (m, 2H), 7.34 (t, 1H, J = 8.1 Hz), 7.10 (t, 1H, J = 2.3 Hz), 6.95 (dd, 1H, J = 7.8, 2.0 Hz), 6.76 (dd, 1H, J = 8.5, 2.5 Hz), 6.45 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.95 (s, 3H), 3.04 (s, 6H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 151.4, 145.9, 145.4, 144.6, 138.1, 130.3, 130.1, 128.0, 127.1, 127.0, 126.8, 122.8, 122.5, 121.8, 121.1, 119.9, 112.5, 112.4, 108.1, 104.6, 76.6, 69.2, 52.5, 40.4, 27.7; ESIMS: m/z 507 [M+Na]+, HRESIMS: calcd for C28H28N4O4Na [M+Na]+ 507.2001, found 507.2003.
1-O-((1-(2,3-dimethylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (30). Yield: 75%, yellow solid, MP: 64–66 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22–8.16 (m, 2H), 7.73 (s, 1H), 7.52 (m, 2H), 7.30 (d, 1H, J = 7.6 Hz), 7.21 (t, 1H, J = 7.7 Hz), 7.15 (d, 1H, J = 7.6 Hz), 6.45 (d, 1H, J = 9.9 Hz), 5.69 (d, 1H, J = 9.9 Hz), 5.36 (s, 2H), 3.96 (s, 3H), 2.36 (s, 3H), 2.00 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.7, 145.4, 143.7, 138.8, 136.6, 132.8, 131.4, 130.3, 128.1, 127.1, 127.0, 126.7, 126.1, 125.3, 124.0, 122.9, 122.4, 121.2, 119.9, 112.4, 76.6, 68.9, 52.5, 27.7, 20.4, 14.3; ESIMS: m/z 492 [M+Na]+, HRESIMS: calcd for C28H27N3O4Na [M+Na]+ 492.1896, found 492.1894.
1-O-((1-(2,5-dimethylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (31). Yield: 58%, yellow solid, MP: 59–61 °C, 1H NMR (CDCl3, 400 MHz) δ 8.33 (dd, 1H, J = 6.5, 3.3 Hz), 8.28 (dd, 1H, J = 6.5, 3.3 Hz), 7.87 (s, 1H), 7.64 (m, 2H), 7.36 (m, 2H), 6.57 (d, 1H, J = 9.9Hz), 5.82 (d, 1H, J = 9.9 Hz), 5.47 (s, 2H), 4.08 (s, 3H), 2.50 (s, 3H), 2.26 (s, 3H), 1.64 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.7, 145.4, 143.7, 136.8, 136.2, 131.3, 130.6, 130.4, 130.3, 128.1, 127.1, 127.0, 126.7, 126.5, 124.9, 122.9, 122.4, 121.2, 119.9, 112.4, 76.6, 68.9, 52.5, 27.7, 20.7, 21.1; ESIMS: m/z 492 [M+Na]+, HRESIMS: calcd for C28H27N3O4Na [M+Na]+ 492.1896, found 492.1894.
1-O-((1-(3,4-dimethylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (32). Yield: 75%, yellow solid, MP: 76–78 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.4, 3.4 Hz), 8.17 (dd, 1H, J = 6.3, 3.3 Hz), 8.04 (s, 1H), 7.52 (m, 3H), 7.43 (dd, 1H, J = 8.0, 3.3 Hz), 7.26 (d, 1H, J = 8.0 Hz), 6.45 (d, 1H, J = 10.0 Hz), 5.70 (d, 1H, J = 10.0 Hz), 5.33 (s, 2H), 3.95 (s, 3H), 2.35 (s, 3H), 2.32 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.9, 145.4, 144.7, 138.4, 137.6, 135.0, 130.7, 130.3, 128.0, 127.1, 127.0, 126.8, 122.8, 122.5, 121.9, 121.5, 121.1, 119.9, 118.0, 112.4, 76.6, 69.2, 52.5, 27.7, 19.9, 19.5; ESIMS: m/z 492 [M+Na]+, HRESIMS: calcd for C28H27N3O4Na [M+Na]+ 492.1896, found 492.1894.
1-O-((1-(5-fluoro-2-methylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (33). Yield: 65%, white solid, MP: 61–63 °C, 1H NMR (CDCl3, 400 MHz) δ 8.21 (dd, 1H, J = 6.4, 3.3 Hz), 8.15 (dd, 1H, J = 6.4, 3.3 Hz), 7.76 (s, 1H), 7.52 (m, 2H), 7.32 (dd, 1H, J = 8.2, 5.9 Hz), 7.17–7.07 (m, 2H), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.35 (s, 2H), 3.95 (s, 3H), 2.16 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 162.0, 159.6, 145.5, 143.9, 132.7, 136.9, 130.3, 129.3, 128.0, 127.1, 127.1, 126.8, 124.9, 122.8, 122.5, 121.2, 119.8, 116.9, 113.5, 112.4, 76.6, 68.7, 52.6, 27.7, 17.4; ESIMS: m/z 472 [M−H]−, HRESIMS: calcd for C27H24N3O4FNa [M−H]− 472.1675, found 472.1678.
1-O-((1-(2-chloro-4-methylphenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (34). Yield: 92%, yellow solid, MP: 55–57 °C, 1H NMR (CDCl3, 400 MHz) δ 8.22 (dd, 1H, J = 6.5, 3.4 Hz), 8.16 (dd, 1H, J = 6.5, 3.3 Hz), 8.00 (s, 1H), 7.51 (m, 3H), 7.38 (s, 1H), 7.23 (d, 1H, J = 8.0 Hz), 6.44 (d, 1H, J = 9.9Hz), 5.69 (d, 1H, J = 9.9 Hz), 5.35 (s, 2H), 3.96 (s, 3H), 2.42 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 145.8, 145.4, 143.8, 141.6, 132.4, 131.0, 130.3, 128.6, 128.3, 128.1, 127.5, 127.1, 127.0, 126.8, 125.5, 122.8, 122.4, 121.1, 119.9, 112.4, 76.6, 68.9, 52.6, 27.7, 21.1; ESIMS: m/z 512 [M+Na]+, HRESIMS: calcd for C27H24N3O4ClNa [M+Na]+ 512.1343, found 512.1348.
1-O-((1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (35). Yield: 20%, white solid, MP: 160–162 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.5, 3.3 Hz), 8.15 (dd, 1H, J = 6.5, 3.3 Hz), 8.07 (s, 1H), 7.71 (d, 2H, J = 8.7 Hz), 7.54–7.48 (m, 4H), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.33 (s, 2H), 3.94 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.8, 145.9, 145.7, 145.4, 135.8, 134.9, 130.5, 130.2, 128.0, 127.4, 127.3, 127.0, 122.9, 122.8, 122.1, 121.7, 121.3, 120.0, 112.6, 76.8, 69.2, 52.7, 27.9; ESIMS: m/z 498 [M+Na]+, HRESIMS: calcd for C26H22N3O4ClNa [M+Na]+ 498.1194, found 498.1191.
1-O-((1-(4-(trifluoromethyl)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (36). Yield: 15%, white solid, MP: 168–170 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.5, 3.3 Hz), 8.15 (m, 2H), 7.93 (d, 2H, J = 8.4 Hz), 7.83 (d, 2H, J = 8.3 Hz), 7.54 (m, 2H), 6.44 (d, 1H, J = 9.9 Hz), 5.71 (d, 1H, J = 9.9 Hz), 5.35 (s, 2H), 3.94 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 150 MHz) δ 167.8, 145.9, 145.7, 145.4, 139.7, 131.2, 130.6, 130.2, 128.1, 127.4, 127.4, 127.3, 127.0, 122.8, 122.8, 122.1, 121.7, 121.6, 121.3, 120.9, 120.0, 112.6, 76.8, 69.1, 52.7, 27.9; ESIMS: m/z 532 [M+Na]+, HRESIMS: calcd for C27H22N3O4F3Na [M+Na]+ 532.1453, found 532.1455.
1-O-((1-(3-(trifluoromethoxy)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (37). Yield: 15%, white solid, MP: 161–163 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.5, 3.3 Hz), 8.15 (dd, 1H, J = 6.4, 3.3 Hz), 8.10 (s, 1H), 7.75–7.66 (m, 2H), 7.59 (t, 1H, J = 8.1 Hz), 7.53 (m, 2H), 7.33 (d, 1H, J = 8.3 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.71 (d, 1H, J = 9.9 Hz), 5.34 (s, 2H), 3.95 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 150 MHz) δ 167.8, 150.2, 145.9, 145.7, 145.6, 138.3, 131.4, 130.5, 128.1, 127.4, 127.3, 127.0, 122.9, 122.8, 121.7, 121.3, 121.2, 120.0, 118.9, 113.9, 112.6, 76.8, 69.2, 52.7, 27.9; ESIMS: m/z 548 [M+Na]+, HRESIMS: calcd for C27H22N3O5F3Na [M+Na]+ 548.1401, found 548.1404.
1-O-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (38). Yield: 20%, white solid, MP: 157–159 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.4, 3.3 Hz), 8.15 (dd, 1H, J = 6.5, 3.3 Hz), 8.08 (s, 1H), 7.81 (d, 2H, J = 8.6 Hz), 7.53 (m, 2H), 7.40 (d, 2H, J = 8.4 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.34 (s, 2H), 3.94 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 149.1, 145.7, 145.5, 145.3, 135.4, 130.3, 127.9, 127.2, 127.1, 126.8, 122.7, 122.6, 122.3, 122.2, 121.6, 121.1, 119.8, 112.4, 76.6, 69.0, 52.5, 27.7; ESIMS: m/z 548 [M+Na]+, HRESIMS: calcd for C27H22N3O5F3Na [M+Na]+ 548.1408, found 548.1404.
1-O-((1-(2,3-dichlorophenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (39). Yield: 70%, yellow solid, MP: 66–68 °C, 1H NMR (CDCl3, 400 MHz) δ 8.21 (dd, 1H, J = 6.4, 3.3 Hz), 8.15 (dd, 1H, J = 6.3, 3.3 Hz), 8.01 (s, 1H), 7.63 (dd, 1H, J = 8.1, 1.6 Hz), 7.56–7.47 (m, 3H), 7.38 (t, 1H, J = 8.1 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.69 (d, 1H, J = 9.9 Hz), 5.36 (s, 2H), 3.96 (s, 3H), 1.52 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.6, 145.4, 143.9, 136.4, 134.6, 131.7, 130.3, 128.2, 128.0, 127.9, 127.1, 127.0, 126.8, 126.3, 125.5, 122.8, 122.5, 121.2, 119.8, 112.4, 76.6, 68.7, 52.5, 27.7; ESIMS: m/z 532 [M+Na]+, HRESIMS: calcd for C26H21N3O4Cl2Na [M+Na]+ 532.0802, found 532.0801.
1-O-((1-(3-chloro-4-fluorophenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (40). Yield: 30%, white solid, MP: 179–181 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.4, 3.4 Hz), 8.13 (dd, 1H, J = 6.4, 3.3 Hz), 8.03 (s, 1H), 7.86 (dd, 1H, J = 6.3, 2.7 Hz), 7.64 (m, 1H), 7.53 (m, 2H), 7.31 (t, 1H, J = 8.6 Hz), 6.44 (d, 1H, J = 9.9 Hz), 5.70 (d, 1H, J = 9.9Hz), 5.33 (s, 1H), 3.94 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.7, 156.8, 145.7, 145.5, 145.3, 133.6, 130.3, 127.8, 127.2, 127.1, 126.8, 123.3, 122.7, 122.6, 121.6, 121.1, 120.5, 119.8, 117.8, 117.6, 112.4, 76.6, 68.9, 52.5, 27.7; ESIMS: m/z 516 [M+Na]+, HRESIMS: calcd for C26H21N3O4FClNa [M+Na]+ 516.1096, found 516.1097.
1-O-((1-(3-chloro-5-(trifluoromethyl)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (41). Yield: 17%, white solid, MP: 171–173 °C, 1H NMR (CDCl3, 400 MHz) δ 8.24 (dd, 1H, J = 6.5, 3.3 Hz), 8.16–8.08 (m, 2H), 8.02 (m, 1H), 7.94 (m, 1H), 7.71 (s, 1H), 7.54 (m, 2H), 6.44 (d, 1H, J = 9.9 Hz), 5.71 (d, 1H, J = 9.9Hz), 5.35 (s, 2H), 3.94 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.8, 145.9, 145.8, 138.4, 136.9, 134.1, 133.8, 130.6, 128.0, 127.4, 127.3, 127.1, 125.9, 124.1, 122.8, 122.7, 121.6, 121.4, 120.0, 115.9, 112.6, 76.8, 69.1, 52.8, 29.9, 27.9; ESIMS: m/z 566 [M+Na]+, HRESIMS: calcd for C27H21N3O4F3ClNa [M+Na]+ 566.1066, found 566.1065.
1-O-((1-(3,5-bis(trifluoromethyl)phenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (42). Yield: 20%, white solid, MP: 160–162 °C, 1H NMR (CDCl3, 400 MHz) δ 8.28–8.10 (m, 3H), 8.19 (s, 1H), 8.12 (dd, 1H, J = 6.5, 3.2 Hz), 7.97 (s, 1H), 7.54 (m, 2H), 6.44 (d, 1H, J = 9.9 Hz), 5.71 (d, 1H, J = 9.9 Hz), 5.36 (s, 2H), 3.94 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.9, 145.6, 145.5, 138.0, 134.2, 133.8, 133.5, 133.2, 130.4, 127.8, 127.2, 127.1, 126.9, 123.9, 122.6, 122.5, 122.3, 121.4, 121.2, 120.6, 119.8, 112.4, 76.6, 68.7, 52.5, 27.7; ESIMS: m/z 600 [M+Na]+, HRESIMS: calcd for C28H21N3O4F6Na [M+Na]+ 600.1327, found 600.1328.
1-O-((1-(4-cyanophenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (43). Yield: 47%, white solid, MP: 167–169 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.4, 3.4 Hz), 8.17 (s, 1H), 8.12 (dd, 1H, J = 6.4, 3.3 Hz), 7.92 (d, 2H, J = 8.7 Hz), 7.84 (d, 2H, J = 8.7 Hz), 7.53 (m, 2H), 6.43 (d, 1H, J = 9.9Hz), 5.70 (d, 1H, J = 9.9 Hz), 5.34 (s, 2H), 3.93 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.7, 145.6, 145.5, 139.8, 134.0, 130.4, 127.8, 127.2, 127.1, 126.8, 122.6, 122.5, 121.2, 121.1, 120.7, 119.8, 117.8, 112.5, 112.4, 76.6, 68.8, 52.5, 27.7; ESIMS: m/z 489 [M+Na]+, HRESIMS: calcd for C29H29N3O4Na [M+Na]+ 489.1536, found 489.1533.
1-O-((1-(3-cyanophenyl)-1H-1,2,3-triazol-4-yl)methyl)-mollugin (44). Yield: 35%, white solid, MP: 187–189 °C, 1H NMR (CDCl3, 400 MHz) δ 8.23 (dd, 1H, J = 6.5, 3.3 Hz), 8.12–8.20 (m, 4H), 7.74 (d, 1H, J = 7.7 Hz), 7.67 (t, 1H, J = 7.9 Hz), 7.53 (m, 2H), 6.43 (d, 1H, J = 9.9 Hz), 5.71 (d, 1H, J = 9.9 Hz), 5.34 (s, 2H), 3.94 (s, 3H), 1.53 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 167.6, 145.6, 145.5, 137.6, 132.2, 130.9, 130.4, 127.8, 127.2, 127.1, 126.8, 124.6, 123.8, 122.6, 121.4, 121.1, 119.8, 117.4, 114.2, 112.4, 76.6, 68.8, 52.5, 27.7; ESIMS: m/z 489 [M+Na]+, HRESIMS: calcd for C27H22N4O4Na [M+Na]+ 489.1532, found 489.1533.