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.