106
Biol. Pharm. Bull.
Vol. 43, No. 1 (2020)
(d, J=15.0Hz, 1H), 2.07–1.96 (m, 4H), 1.91 (dd, J=13.2, 3H), 1.28–1.24 (m, 1H), 1.12 (s, 3H), 1.02 (s, 3H), 0.99 (s, 1H).
10.4Hz, 1H), 1.80 (td, J=13.5, 4.3Hz, 1H), 1.63 (qd, J=13.3, 13C-NMR (101MHz, CDCl3) δ: 200.07, 176.27, 169.12, 149.26,
7.3Hz, 5H), 1.52–1.43 (m, 2H), 1.40 (t, J=7.0Hz, 4H), 147.99, 130.66, 130.62, 130.17, 128.50, 127.60, 127.56, 121.27,
1.35 (s, 3H), 1.34–1.29 (m, 1H), 1.29–1.22 (m, 2H), 1.19 (t, 118.99, 118.74, 115.02, 114.00, 78.77, 77.25, 66.10, 64.70, 64.66,
J=7.9Hz, 1H), 1.14 (d, J=4.6Hz, 6H), 1.11 (s, 3H), 1.00 64.62, 61.80, 54.93, 48.17, 45.34, 43.98, 43.17, 41.10, 39.14,
(s, 3H), 0.96 (dd, J=12.4, 4.3Hz, 1H), 0.80 (s, 3H), 0.72 (s, 37.65, 37.08, 32.74, 31.74, 31.20, 28.46, 28.24, 28.10, 27.31,
3H), 0.66 (d, J=13.4Hz, 1H). 13C-NMR (101MHz, CDCl3) δ: 26.45, 26.39, 23.39, 18.66, 17.48, 16.37, 15.59. HRMS (ESI+):
200.04, 176.27, 169.10, 150.13, 148.71, 137.21, 132.53, 130.77, Calculated for C46H61BrFO5 (M+H)+: 807.3630, found:
130.24, 128.55, 128.39, 121.45, 117.37, 114.83, 78.77, 77.24, 809.3735 (M+2+H)+.
67.31, 66.12, 64.99, 61.80, 54.95, 48.13, 45.34, 43.98, 43.18,
41.13, 39.14, 37.67, 37.09, 32.76, 31.75, 31.22, 28.46, 28.25, (6g)
28.11, 27.32, 26.46, 26.42, 23.39, 18.67, 17.49, 16.37, 15.59,
4-((2-Fluorobenzyl)oxy)-3-methoxybenzyl Glycyrrhetinate
1
White solid. Y=85%. H-NMR (400MHz, CDCl3) δ: 7.54
14.90. HRMS (ESI+): Calculated for C46H61Cl2O6 (M+H)+: (dt, J=7.5, 3.8Hz, 1H), 7.32–7.24 (m, 1H), 7.13 (t, J=7.2Hz,
779.3845, found: 779.3865.
4-((2,6-Dichlorobenzyl)oxy)-3,5-dimethylbenzyl J=8.2, 1.7Hz, 1H), 5.59 (s, 1H), 5.20 (s, 2H), 5.10–5.02 (m,
Glycyrrhetinate (6d) 2H), 4.10 (q, J=7.0Hz, 2H), 3.22 (dd, J=10.7, 5.6Hz, 1H),
1H), 7.10–7.03 (m, 1H), 6.92 (dd, J=4.9, 3.2Hz, 2H), 6.88 (dd,
1
White solid. Y=75%. H-NMR (400MHz, CDCl3) δ: 7.36 2.79 (dt, J=13.3, 3.3Hz, 1H), 2.32 (s, 1H), 2.08–1.96 (m, 3H),
(d, J=8.0Hz, 2H), 7.24 (dd, J=8.6, 7.4Hz, 1H), 7.02 (s, 2H), 1.91 (dt, J=20.6, 10.9Hz, 1H), 1.80 (td, J=13.5, 4.2Hz, 1H),
5.56 (s, 1H), 5.19–5.12 (m, 3H), 4.97 (d, J=11.9Hz, 1H), 3.23 1.72–1.54 (m, 7H), 1.50–1.37 (m, 5H), 1.35 (s, 3H), 1.31 (dd,
(dd, J=10.7, 5.6Hz, 1H), 2.80 (dt, J=13.3, 3.3Hz, 1H), 2.34 J=8.1, 5.1Hz, 1H), 1.28–1.22 (m, 2H), 1.18 (t, J=8.3Hz, 1H),
(s, 6H), 2.03 (dd, J=20.3, 7.4Hz, 3H), 1.97–1.90 (m, 1H), 1.13 (d, J=1.1Hz, 6H), 1.10 (s, 3H), 1.00 (s, 3H), 0.95 (dd,
1.81 (td, J=13.6, 4.3Hz, 1H), 1.64 (dt, J=19.6, 8.5Hz, 5H), J=12.4, 4.2Hz, 1H), 0.80 (s, 3H), 0.71 (s, 3H), 0.68 (s, 1H).
1.52 (s, 1H), 1.48–1.39 (m, 3H), 1.36 (s, 3H), 1.33–1.24 (m, 13C-NMR (101MHz, CDCl3) δ: 200.07, 176.29, 169.14, 149.23,
3H), 1.17 (s, 3H), 1.16 (s, 1H), 1.13 (s, 3H), 1.11 (s, 3H), 1.01 148.32, 129.86, 129.54, 129.50, 129.44, 129.36, 128.52, 124.20,
(s, 4H), 0.99–0.95 (m, 1H), 0.81 (s, 3H), 0.74 (s, 3H), 0.70 124.16, 121.33, 115.26, 115.05, 114.86, 114.10, 78.76, 77.26,
(d, J=10.5Hz, 1H). 13C-NMR (101MHz, CDCl3) δ: 199.99, 66.15, 64.69, 61.80, 54.93, 48.14, 45.34, 43.98, 43.17, 41.10,
176.30, 169.07, 155.53, 137.09, 132.96, 131.80, 131.67, 130.30, 39.14, 37.67, 37.08, 32.75, 31.74, 31.20, 28.46, 28.25, 28.11,
129.15, 128.59, 128.50, 78.76, 77.37, 77.26, 77.05, 76.74, 68.63, 27.31, 26.45, 26.40, 23.39, 18.66, 17.49, 16.37, 15.60. HRMS
65.94, 61.78, 54.94, 48.10, 45.30, 43.93, 43.17, 41.12, 39.14, (ESI+): Calculated for C46H62FO6 (M+H)+: 729.4530, found:
37.64, 37.07, 32.75, 31.73, 31.25, 28.45, 28.25, 28.11, 27.32, 729.4551.
26.47, 26.42, 23.37, 18.69, 17.49, 16.78, 16.36, 15.60. HRMS
(ESI+): Calculated for C46H61Cl2O5 (M+H)+: 763.3896, found:
763.3907.
2′,4′-Dichlorobenzyl Glycyrrhetinate (7a)
White solid. Y=90%. H-NMR (400MHz, CDCl3) δ: 7.42
(d, J=2.0Hz, 1H), 7.38 (d, J=8.3Hz, 1H), 7.28 (dd, J=8.3,
1
4 -((2,4 -Dichlorobenzyl)oxy)-3,5-dimethylbenzyl 2.0Hz, 1H), 5.60 (s, 1H), 5.19 (s, 2H), 4.09 (dd, J=19.4,
Glycyrrhetinate (6e) 12.3Hz, 1H), 3.21 (dt, J=24.7, 12.4Hz, 1H), 2.83–2.70 (m,
1
White solid. Y=71%. H-NMR (400MHz, CDCl3) δ: 7.67 1H), 2.33 (s, 1H), 2.12–1.88 (m, 7H), 1.81 (tt, J=17.5, 8.8Hz,
(d, J=8.4Hz, 1H), 7.41 (d, J=2Hz, 1H), 7.32 (dd, J=2Hz, 1H), 1.71–1.53 (m, 5H), 1.43 (dd, J=23.7, 11.8Hz, 3H), 1.36
8.4Hz, 1H),7.05 (s, 2H), 5.48 (s, 1H), 5.30 (s, 1H), 5.20 (d, (s, 3H), 1.31 (t, J=5.2Hz, 1H), 1.28–1.23 (m, 3H), 1.18 (s,
J=12Hz, 1H), 4.92 (d, J=12Hz, 1H), 4.84 (s, 2H), 3.22 3H), 1.12 (d, J=6.3Hz, 6H), 1.00 (s, 3H), 0.95 (dd, J=13.0,
(q, J=5.6Hz, 10.8Hz, 1H), 2.80–2.75 (m, 1H), 2.29 (s, 6H), 4.1Hz, 1H), 0.81 (s, 3H), 0.77 (s, 3H), 0.70 (d, J=11.3Hz,
2.05–1.89 (m, 5H), 1.83–1.76 (m, 1H), 1.66–1.52 (m, 7H), 1H). 13C-NMR (101MHz, CDCl3) δ: 200.10, 175.94, 168.94,
1.52–1.36 (m, 3H), 1.34 (s, 3H), 1,32–1.24 (m, 3H), 1.16 (s, 134.78, 134.43, 132.27, 130.92, 129.45, 128.53, 127.25, 78.53,
3H), 1.11 (s, 3H), 1.09 (s, 3H), 1.00 (s, 3H), 0.80 (s, 3H), 0.73 63.09, 61.76, 60.36, 54.88, 48.15, 45.32, 44.12, 43.14, 40.95,
(s, 3H), 0.68 (d, J=10.4Hz, 1H); 13C-NMR (101MHz, CDCl3) 39.12, 37.65, 37.02, 32.71, 31.76, 31.08, 28.44, 28.32, 28.10,
δ: 200.03, 176.29, 169.08, 155.49, 134.19, 134.00, 133.11, 27.21, 26.39, 26.34, 23.36, 21.02, 18.63, 17.45, 15.63. HRMS
132.05, 131.38, 129.84, 129.21, 129.06, 128.41, 127.29, 78.76, (ESI+): Calculated for C37H50Cl2O6 (M+H)+: 629.3164, found:
77.25, 70.14, 65.92, 61.78, 54.92, 48.18, 45.29, 43.94, 43.16, 629.3173.
41.14, 39.13, 39.11, 37.63, 37.05, 32.73, 31.74, 31.24, 28.42,
28.23, 28.10, 27.30, 26.47, 26.40, 23.35, 18.67, 17.48, 16.37,
2′,6′-Dichlorobenzyl Glycyrrhetinate (7b)
1
White solid. Y=88%. H-NMR (400MHz, CDCl3) δ: 7.38
15.59. HRMS (ESI+): Calculated for C46H61Cl2O5 (M+H)+: (d, J=8.2Hz, 2H), 7.30–7.26 (m, 1H), 5.48–5.41 (m, 2H), 5.34
763.3896, found: 763.3911.
4-((4-Bromo-2-f luorobenzyl)oxy)-3-ethoxybenzyl 1H), 2.76 (dt, J=13.3, 3.3Hz, 1H), 2.29 (s, 1H), 2.20–2.07 (m,
Glycyrrhetinate (6f) 1H), 2.06–1.94 (m, 3H), 1.92–1.75 (m, 2H), 1.66–1.55 (m, 6H),
(d, J=11.6Hz, 1H), 5.30 (s, 1H), 3.19 (dt, J=35.7, 17.9Hz,
1
White solid. Y=75%. H-NMR (CDCl3, 400MHz) δ: 7.74 1.38 (dd, J=11.7, 9.3Hz, 4H), 1.32 (s, 3H), 1.26 (t, J=7.1Hz,
(t, J=8.4Hz, 1H), 7.61–7.55 (m, 3H), 7.20 (s, 2H), 5.88 (s, 1H), 1.17 (s, 3H), 1.12 (d, J=5.9Hz, 6H), 0.99 (s, 3H), 0.93
1H), 5.46 (s, 2H), 5.38 (q, J=24Hz, 12Hz, 2H), 4.40 (q, (dd, J=13.1, 4.6Hz, 1H), 0.80 (s, 3H), 0.67 (t, J=9.2Hz, 1H).
J=12Hz, 8Hz, 2H), 3.56–3.51 (m, 1H), 3.12–3.07 (m, 1H), 13C-NMR (101MHz, CDCl3) δ: 200.16, 176.11, 169.02, 136.85,
2.63 (s, 1H), 2.36–2.28 (m, 3H), 2.25–2.20 (m, 1H), 2.14–2.07 131.47, 130.73, 128.52, 128.47, 78.73, 61.76, 61.37, 60.41,
(m, 1H), 2.02–1.87 (m, 6H), 1.77–1.72 (m, 5H), 1.70–1.68 54.90, 48.25, 45.33, 44.31, 43.13, 40.94, 39.13, 37.66, 37.04,
(m, 1H), 1.66 (s, 3H), 1.64–1.61 (m, 1H), 1.59–1.57 (m, 2H), 32.75, 31.81, 31.14, 28.44, 28.38, 28.10, 27.28, 26.48, 26.38,
1.55–1.49 (m, 1H), 1.44 (d, J=4Hz, 6H), 1.41 (s, 3H), 1.31 (s, 23.30, 18.67, 17.48, 16.38, 15.59. HRMS (ESI+): Calculated for