5
92 Medicinal Chemistry, 2018, Vol. 14, No. 6
Zhang et al.
(
C21), 166.06, 138.93 (C19), 136.18, 134.67, 131.50,
29.83, 127.43, 125.27, 117.26 (C20), 74.60 (C11), 69.96
C14), 58.13 (C4), 45.43 (C9), 44.92 (C13), 43.95 (C12),
1.77 (C5), 38.69 (C22), 36.68 (C6), 36.00 (C10), 34.53
C2), 34.43, 33.10, 30.40 (C8), 26.83 (C7), 26.36 (C18),
4.85 (C1), 16.86 (C16), 14.85 (C15), 11.56 (C17); IR (KBr,
3.2.11.
22-(2-(3-Methy-benzoylamino)-ethylsulfanyl)-22-
1
deoxypleuromutilin (10b)
(
White powder; yield: 49.45%; mp: 53.4-54.0°C; 1H-
4
NMR spectrum (600MHz, Chloroform-d) ꢀ 7.67 (1H, m,
J=1.6, 0.9Hz), 7.61 (1H, m), 7.33 (2H, m), 6.47 (1H, dd,
J=17.4, 11.0Hz, H19), 5.77 (1H, d, J=8.5Hz, H14), 5.29 (1H,
dd, J=11.0, 1.5Hz, H20), 5.19 (1H, dd, J=17.4, 1.5Hz, H20),
3.71 (1H, dd, J=14.1, 6.0Hz), 3.62 (1H, m), 3.37 (1H, d,
J=6.6Hz, H11), 3.24 (1H, d, J=15.5Hz, H22), 3.22 (1H, s,
H22), 2.87 (2H, m), 2.42 (3H, s), 2.22 (5H, m, H2, H4, H10,
H13), 1.78 (1H, dd, J=14.5, 3.1Hz, H6), 1.59 (6H, m), 1.46
(3H, s, H15), 1.36 (2H, m, H13.H18), 1.17 (3H, s, H18),
(
2
-
1
cm ) 3382, 2933, 2882, 1724, 1645, 1570, 1538, 1470, 1414,
1
6
5
374, 1283, 1189, 1151, 1116, 1017, 980, 953, 939, 917, 749,
+
80; HR-MS (ESI): Cal for
76.2545; Found: 576.2569.
31 5
C H43NClO S (M-H ):
3
.2.9.
22-(2-(4-Chloro-benzoylamino)-ethylsulfanyl)-22-
deoxypleuromutilin (9c)
1
.13 (1H, dd, J=14.1, 4.5Hz, H8), 0.90 (3H, d, J=7.0Hz,
White powder; yield: 44.44%; mp: 75.9-76.7°C; 1H-
13
H17), 0.74 (3H, d, J=7.1Hz, H16); C NMR (151MHz,
Chloroform-d) ꢀ 216.91 (C3), 169.39 (C21), 167.61, 138.94
NMR spectrum (600MHz, Chloroform-d) ꢀ 8.04 (1H, m),
7
.82 (2H, m), 7.47 (1H, m), 7.43 (2H, m), 6.45 (1H, dd,
(
C19), 138.39, 134.34, 132.25, 128.39, 127.82, 123.94,
J=17.4, 11.0Hz, H19), 5.77 (1H, d, J=8.5Hz, H14), 5.27 (1H,
dd, J=11.0, 1.5Hz, H20), 5.20 (1H, dd, J=17.4, 1.5Hz, H20),
1
17.28 (C20), 74.60 (C11), 69.75 (C14), 58.15 (C4), 45.44
C9), 44.90 (C13), 43.94 (C12), 41.77 (C5), 38.43 (C22),
6.71 (C6), 36.02 (C10), 34.44 (C2), 34.30, 33.06, 30.41
(
3
3
2
.73 (1H, m), 3.60 (1H, m), 3.38 (1H, d, J=6.5Hz, H11),
.25 (1H, d, J=15.7Hz, H22), 3.21 (1H, d, J=15.7Hz, H22),
.87 (2H, dd, J=6.9, 5.3Hz), 2.20 (6H, m, H2, H4, H10,
3
(
C8), 26.84 (C7), 26.35 (C18), 24.85 (C1), 21.39, 16.86
-1
(C16), 14.87 (C15), 11.53 (C17); IR (KBr, cm ) 3394, 2933,
286, 1725, 1643, 1606, 1585, 1539, 1484, 1455, 1413, 1374,
1283, 1191, 1152, 1117, 1086, 1019, 981, 953, 939, 917, 745,
H13), 1.79 (1H, dd, J=14.6, 3.2Hz, H6), 1.59 (5H, m, H1,
H7), 1.47 (3H, s, H15), 1.34 (3H, m, H13.H18, 11-OH), 1.18
+
(
3H, s, H18), 1.14 (1H, dd, J=14.1, 4.5Hz, H8), 0.92 (3H, d,
689; HR-MS (ESI): Cal for C H NO S (M-H ): 556.3091;
3
2
46
5
1
3
J=7.0Hz, H17), 0.73 (3H, d, J=7.1Hz, H16); C NMR
151MHz, Chloroform-d) ꢀ 216.87 (C3), 169.72 (C21),
Found: 556.3107.
(
3
.2.12.
22-(2-(4-Methy-benzoylamino)-ethylsulfanyl)-22-
1
1
5
66.34, 138.91 (C19), 137.76, 132.73, 131.50, 128.83,
28.77, 128.55, 117.29 (C20), 74.60 (C11), 69.98 (C14),
8.12 (C4), 45.44 (C9), 44.89 (C13), 43.95 (C12), 41.77
deoxypleuromutilin (10c)
White powder; yield: 36.45%; mp: 56.9-57.6°C; 1H-
NMR spectrum (600MHz, Chloroform-d) ꢀ 7.73 (2H, d,
J=7.9Hz), 6.95 (1H, m), 6.47 (1H, dd, J=17.4, 11.0Hz, H19),
5.77 (1H, d, J=8.5Hz, H14), 5.29 (1H, dd, J=11.0, 1.5Hz,
H20), 5.19 (1H, dd, J=17.4, 1.5Hz, H20), 3.71 (2H, m), 3.60
(1H, m), 3.37 (1H, d, J=6.6Hz, H11), 3.22 (1H, s, H22), 3.21
(
C5), 38.64 (C22), 36.6 (C6), 36.04 (C10), 34.50 (C2),
4.43, 33.15, 30.40 (C8), 26.84 (C7), 26.36 (C18), 24.84
3
-
1
(
C1), 16.88 (C16), 14.86 (C15), 11.55 (C17); IR (KBr, cm )
3
1
9
370, 2931, 2863, 1727, 1647, 1593, 1570, 1537, 1486, 1455,
417, 1374, 1281, 1176, 1150, 1114, 1092, 1015, 979, 952,
(
1H, s, H22), 2.86 (2H, dd, J=9.6, 4.2Hz), 2.22 (5H, m, H2,
5
37, 916, 849, 760; HR-MS (ESI): Cal for C31H43NClO S
+
H4, H10, H13), 1.78 (1H, dd, J=14.6, 3.2Hz, H6), 1.6 (6H,
m), 1.46 (3H, s, H15), 1.36 (2H, m, H13.H18), 1.17 (3H, s,
H18), 1.13 (1H, dd, J=14.1, 4.4Hz, H8), 0.90 (3H, d,
(
M-H ): 576.2545; Found: 576.2568.
3
.2.10.
22-(2-(2-Methy-benzoylamino)-ethylsulfanyl)-22-
deoxypleuromutilin(10a)
13
J=6.9Hz, H17), 0.74 (3H, d, J=7.1Hz, H16); C NMR
White powder; yield: 50.33%; mp: 55.4-56.1°C; 1H-
(
151MHz, Chloroform-d) ꢀ 216.93 (C3), 169.42 (C21),
1
41.91, 138.95 (C19), 129.18, 127.03, 117.27 (C20), 74.59
C11), 69.77 (C14), 58.15 (C4), 45.44 (C9), 44.89 (C13),
3.95 (C12), 41.76 (C5), 38.42 (C22), 36.72 (C6), 36.02
C10), 34.44 (C2), 34.30, 33.09, 30.42 (C8), 26.84 (C7),
NMR spectrum (600MHz, Chloroform-d) ꢀ 7.66 (1H, s),
(
7
.61 (1H, m), 7.43 (2H, m), 6.47 (1H, dd, J=17.4, 11.0Hz,
4
H19), 5.77 (1H, d, J=8.5Hz, H14), 5.29 (1H, dd, J=11.0,
(
1
.4Hz, H20), 5.19 (1H, dt, J=17.5, 1.0Hz, H20), 3.71 (1H,
2
1
1
1
7
6.37 (C18), 24.84 (C1), 21.47, 16.88 (C16), 14.87 (C15),
dq, J=12.1, 6.0Hz), 3.64 (1H, m), 3.37 (1H, d, J=6.5Hz,
-1
1.55 (C17); IR (KBr, cm ) 3407, 2933, 2864, 1731, 1637,
540, 1505, 1455, 1415, 1374, 1282, 1230, 1190, 1153, 1118,
088, 1053, 1019, 982, 952, 916, 881, 844, 810, 774, 750,
H11), 3.23 (1H, s, H22), 3.22 (1H, s, H22), 2.87 (2H, m),
2
.42 (2H, s), 2.21 (6H, m, H2, H4, H10, H13), 1.78 (1H, dd,
J=14.5, 3.2Hz, H6), 1.59 (5H, m), 1.46 (3H, s, H15), 1.33
3H, m, H13, H18, 11-OH), 1.17 (3H, s, H18), 1.13 (1H, dd,
J=14.2, 4.4Hz, H8), 0.90 (3H, d, J=7.0Hz, H17), 0.74 (3H, d,
05, 669; HR-MS (ESI): Cal for
32 5
C H46NO S (M-
(
+
H ):556.3091; Found: 556.3118.
1
3
J=7.1Hz, H16); C NMR (151MHz, Chloroform-d) ꢀ
3
.2.13. 22-(2-(2-Methoxy-benzoylamino)-ethylsulfanyl)-22-
2
1
16.90 (C3), 169.38 (C21), 167.59, 138.94 (C19), 138.38,
34.35, 132.24, 128.39, 127.82, 123.94, 117.28 (C20), 74.60
deoxypleuromutilin (11a)
White powder; yield: 54.74%; mp: 57.9-59.5°C; 1H-
NMR spectrum (600MHz, Chloroform-d) ꢀ 8.20 (1H, dd,
J=7.8, 1.8Hz), 7.46 (1H, m), 7.08 (1H, m), 6.98 (1H, d,
J=8.3Hz), 6.47 (1H, dd, J=17.4, 11.0Hz, H19), 5.77 (1H, d,
J=8.5Hz, H14), 5.32 (1H, dd, J=11.0, 1.5Hz, H20), 5.19 (1H,
dd, J=17.4, 1.5Hz, H20), 3.99 (3H, s), 3.69 (2H, m), 3.36
(
C11), 69.75 (C14), 58.15 (C4), 45.44 (C9), 44.90 (C13),
4
3.94 (C12), 41.77 (C5), 38.42 (C22), 36.71 (C6), 36.02
(
C10), 34.44 (C2), 34.30, 33.07, 30.41 (C8), 26.84 (C7),
2
1
1
1
6.36 (C18), 24.85 (C1), 21.39, 16.87 (C16), 14.87 (C15),
-1
1.53 (C17); IR (KBr, cm ) 3384, 2930, 2860, 1724, 1644,
606, 1585, 1538, 1455, 1413, 1383, 1282, 1215, 1189, 1150,
(
1H, d, J=6.6Hz, H11), 3.22 (2H, s, H22), 2.87 (2H, t,
116, 1017, 980, 953, 939, 916, 744, 689; HR-MS (ESI): Cal
+
J=6.4Hz), 2.22 (5H, m, H2, H4, H10, H13), 1.78 (1H, dd,
for C32
H
46NO
5
S (M-H ): 556.3091; Found: 556.3110.