Synthesis of AG1, UG1 and DG1
The compound NG1 was prepared by using BINDFOH (0.300 g, 0.391 mmol) dissolved in 250 ml DCE dropped into Th (32.9 mg 0.391 mmol) and BF3∙Et2O (0.523 mL, 1.9 mmol) scattered in 150 ml DCE with a speed of 1 drop per second. The reaction mixture was stirred at r.t. for 30 min. The mixture was extracted over three times with CH2Cl2 and the organic layer was dried over MgSO4, filtered and the solvent was removed under reduced pressure. Purification by silica gel column chromatography (petroleum ether : CH2Cl2= 8:1, continuously increase solvent polarity) to afford AG1 (30 mg, 9%), UG1 (28 mg, 9%) and DG1 (160 mg, 51%) as white powders.
AG1 (yield 9%).1H NMR (400 MHz, CDCl3) δ 7.98 – 7.96 (d, J = 8.4 Hz, 2H), 7.89 – 7.87 (d, J = 8.4 Hz, 2H), 7.55 – 7.45 (m, 12H), 7.38 – 7.33 (m, 2H), 7.35 – 7.33 (d, J = 8.4 Hz, 2H), 7.25 – 7.18 (m, 10H), 6.99 – 6.97 (d, J = 8.0 Hz, 2H), 6.65 (s, 2H), 6.47 – 6.45 (dd, J = 8.0 Hz, 1.6 Hz, 2H), 6.18 (s, 2H).13C NMR (100 MHz, CDCl3) δ 153.0, 152.7, 150.7, 142.7, 141.4, 139.7, 139.3, 136.9,135.3, 133.9, 132.0, 129.7, 128.4, 128.2, 127.9, 127.7, 127.3, 127.0, 126.8, 125.6, 125.3, 124.2, 120.1, 118.8, 64.1 ppm. MALDI-ToF-MS (m/z): calcd. For C62H38S: 814.26 [M+]; Found: 814.66.
UG1 (yield 9%). 1H NMR (400 MHz, CDCl3) δ 7.86 – 7.81 (t, J = 8.4 Hz, 4H), 7.67 – 7.65 (d, J = 7.2 Hz, 2H), 7.49 – 7.46 (t, J = 6.4 Hz, 2H), 7.41 – 7.40 (d, J = 7.6 Hz, 2H), 7.37 – 7.30 (m, 10H), 7.24 – 7.22 (d, J = 6.8 Hz, 2H), 7.16 – 7.13 (t, J = 7.2 Hz, 2H), 7.09 – 7.04 (dd, J = 7.2 Hz, 5.2 Hz, 6H), 6.85 (s, 2H), 6.74 – 6.65 (m, 8H), 5.96 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 150.2, 148.7, 147.8, 143.9, 140.1, 138.5, 138.4, 136.8, 133.5, 133.1, 131.4, 128.3, 127.9, 127.0, 126.4, 125.6, 125.3, 125.1, 124.9, 124.8, 124.5, 123.1, 119.0, 60.8 ppm. MALDI-ToF-MS (m/z): calcd. For C66H42S2: 898.27 [M+]; Found: 898.00.
DG1 (yield 51%). 1H NMR (400 MHz, CDCl3) δ 8.00 – 7.98 (d, J = 8.0 Hz, 2H), 7.73 (s, 4H), 7.57 – 7.52 (m, 5H), 7.48 – 7.46 (d, J = 6.4 Hz, 5H), 7.37 – 7.34 (m, 17H), 7.09 (m, 24H), 6.72 – 6.61 (m, 15H), 6.53 (s, 2H), 6.42 – 6.40 (d, J = 7.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 150.4, 148.9, 144.1, 143.0, 139.5, 138.7, 137.8, 136.6, 133.7, 133.5, 132.7, 132.5, 131.2,130.9, 128.2, 127.8, 127.1, 127.0, 126.8, 126.6, 126.3, 125.7, 125.3, 124.6, 124.1, 122.0, 119.3, 118.8, 61.0 ppm. MALDI-ToF-MS (m/z): calcd. For C124H76S2: 1628.54 [M+]; Found: 1629.44.