Molecules 2021, 26, 2102
9 of 15
(C-9), 50.3 (C-18), 50.1 (C-33), 47.4 (C-19), 47.0 (C-36), 42.6 (C-14), 40.9 (C-8), 39.2 (C-13),
3
8.5 (C-22), 38.5 (C-1), 37.9 (C-10), 37.2 (C-4), 34.4 (C-7), 33.9 (C-16), 33.8 (C-34, C-38), 31.5
(
(
C-35, C-37), 31.0 (C-21), 29.5 (C-15), 28.1 (C-23), 25.7 (C-12), 23.8 (C-2), 21.4 (C-32), 21.1
C-11), 19.6 (C-30), 18.3 (C-6), 16.6 (C-24), 16.4 (C-25), 16.3 (C-26), 14.7 (C-27) ppm; MS (ESI,
− −
MeOH/CHCl , 4:1): m/z 593.3 (100%, [M
for C H N O (594.91): C 76.72, H 10.50, N 4.71; found: C 76.47, H 10.89, N 4.43.
−
H] ), 629.3 (80%, [M + Cl] ); analysis calcd
3
38
62
3
4
(3β)-28-[(Cis-4-Aminocyclohexyl)Amino]-28-Oxolup-20(29)-En-3-Yl Acetate (14). Following
GPB, compound 14 (0.39 g, 65%) was obtained as a colorless solid; R = 0.634 (CHCl /
f
3
◦
20
D
◦
MeOH, 8:2); m.p.: 230–235 C (decomp.);
1
α
= +9.7 (c 0.19, MeOH); IR (ATR):
ν
= 2940 s,
−
1 1
731 m, 1620 m, 1505 m, 1368 m, 1244 s, 1027 m, 978 m, 751 s cm ; H NMR (500 MHz,
CDCl3): = 4.73 (s, 1H, 29-H ), 4.59 (s, 1H, 29-H ), 4.46 (dd, J = 10.3, 5.7 Hz, 1H, 3-H),
.00 (s, 1H, 36-H), 3.47 (s, 1H, 33-H), 3.10 (td, J = 11.0, 3.9 Hz, 1H, 19-H), 2.46 (dd, J = 11.7,
.0 Hz, 1H, 13-H), 2.03 (s, 3H, 32-H), 2.02–1.05 (m, 28H, 37-H, 35-H, 38-H, 34-H, 1-H
2-H , 12-H , 2-H, 18-H, 16-H, 15-H , 6-H, 11-H, 7-H, 1-H , 21-H , 9-H, 15-H ), 1.67 (s,
H, 30-H), 1.03–0.96 (m, 2H, 1-H , 12-H ), 0.95 (s, 3H, 27-H), 0.92 (s, 3H, 26-H), 0.84 (s, 6H,
δ
a
b
4
2
2
3
2
δ
5
3
a
,
a
a
a
b
a
b
a
b
1
3
3-H, 24-H), 0.83 (s, 3H, 25-H), 0.80–0.75 (m, 1H, 5-H) ppm; C NMR (126 MHz, CDCl3):
= 175.6 (C-28), 171.0 (C-31), 150.8 (C-20),109.5 (C-29), 80.9 (C-3), 55.6 (C-17), 55.4 (C-5),
0.5 (C-9), 50.0 (C-18), 48.0 (C-33), 46.7 (C-19), 44.3 (C-36), 42.4 (C-14), 40.8 (C-8), 38.5 (C-22),
8.4 (C-1), 37.8 (C-10), 37.7 (C-13), 37.1 (C-4), 34.4 (C-7), 33.8 (C-16), 30.9 (C-21), 29.7 (C-34,
C-38), 29.4 (C-15), 27.9 (C-23), 26.9 (C-35, C-37), 25.6 (C-12), 23.7 (C-2), 21.3 (C-32), 21.0
(
C-11), 19.5 (C-30), 18.0 (C-6), 16.5 (C-24), 16.3 (C-26), 16.2 (C-25), 14.6 (C-27) ppm; MS (ESI,
+
MeOH/CHCl , 4:1): m/z 595.5 (100%, [M + H] ); analysis calcd for C H N O (594.91):
3
38 62
3
4
C 76.72, H 10.50, N 4.71; found: C 76.55, H 10.83, N 4.61.
(3β)-28-[(trans-4-Aminocyclohexyl)amino]-20,28-dioxo-30-norlupan-3-yl acetate (15). Follow-
ing GPB, compound 15 (0.385 g, 65%) was obtained as a colorless solid; R = 0.595
f
◦
20
D
◦
17.0 (c 0.15, MeOH); IR (ATR):
(
ν
CHCl /MeOH, 8:2); m.p.: 251–255 C (decomp.);
α
=
−
3
−
1 1
= 3384 w, 2941 s, 1710 m, 1633 m, 1516 m, 1368 m, 1025 m, 751 s cm ; H NMR (500 MHz,
= 4.49–4.41 (m, 1H, 3-H), 3.84–3.71 (m, 1H, 35-H), 3.46–3.27 (m, 1H, 19-H), 3.25–
.97 (m, 1H, 32-H), 2.33–2.18 (m, 1H, 13-H), 2.15 (s, 3H, 29-H), 2.07 (d, J = 15.8 Hz, 2H, 18-H,
1-H ), 2.03 (s, 3H, 31-H), 1.94–1.81 (m, 1H, 16-H ), 1.77–1.04 (m, 27-H, 36-H, 34-H, 37-H,
3-H, 22-H, 12-H, 2-H, 1-H , 16-H , 21-H , 15-H , 6-H, 11-H, 7-H, 9-H, 15-H ), 0.98 (s, 3H,
7-H), 0.96–0.92 (m, 1H, 1-H ), 0.90 (s, 3H, 26-H), 0.83–0.82 (m, 6H, 24-H, 25-H), 0.81 (s, 3H,
CDCl3):
δ
2
2
3
2
2
a
a
a
b
b
a
b
b
1
3
3-H), 0.80–0.76 (m, 1H, 5-H) ppm; C NMR (126 MHz, CDCl3):
δ = 212.8 (C-20), 175.8
(C-28), 171.1 (C-30), 80.9 (C-3), 55.5 (C-5), 55.4 (C-17) 51.3 (C-19), 50.5 (C-9), 50.3 (C-33), 50.2
(C-18), 47.0 (C-36), 42.4 (C-14), 40.9 (C-8), 38.5 (C-1), 38.2 (C-22), 37.9 (C-10), 37.3 (C-4), 37.0
(C-13), 34.4 (C-7), 33.1 (C-16), 30.9 (C-33, C-37), 30.3 (C-29), 29.7 (C-36, C-34), 29.6 (C-15),
28.7 (C-21), 28.1 (C-23), 27.3 (C-12), 23.8 (C-2), 21.4 (C-31), 21.1 (C-11), 18.3 (C-6), 16.6 (C-24),
1
6.3 (C-25), 16.3 (C-26), 14.8 (C-27) ppm; MS (ESI, MeOH/CHCl 4:1): m/z 597.4 (100%,
3
+
[M + 2H] ); analysis calcd for C H N O (596.88): C 74.45, H 10.13, N 4.69; found: C
37
60
2
4
74.19, H 10.32, N 4.42.
(
3
β
)-28-[(cis-4-Aminocyclohexyl)amino]-20,28-dioxo-30-norlupan-3-yl acetate (16). Following
GPB, compound 16 (465 mg, 78%) was obtained as a colorless solid; R = 0.65 (CHCl /MeOH,
f
3
◦
20
D
◦
8
:2); m.p.: 257–260 C (decomp.);
α
=
−
9.1 (c 0.14, CHCl ); IR (ATR):
ν
= 2936 m, 1729
3
−
1 1
m, 1600 s, 1517 m, 1369 m, 1245 s, 988 s, 804 m, 7451 m cm ; H NMR (500 MHz, CDCl ):
3
δ
= 4.58–4.26 (m, 1H, 3-H), 4.00–3.83 (m, 1H, 35-H), 3.43 (dt, J = 11.4, 6.0 Hz, 1H, 19-H),
.11–2.85 (m, 1H, 32-H), 2.21 (dt, J = 11.8, 4.5 Hz, 1H, 13-H), 2.14 (s, 3H, 29-H), 2.09–2.03
3
a
b
(m, 2H, 18-H, 21-H ), 2.01 (s, 3H, 31-H), 1.95–1.85 (m, 1H, 16-H ), 1.77–1.01 (m, 27-H, 36-H,
3
3
3
4-H, 37-H, 33-H, 22-H, 12-H, 2-H, 1-H , 16-H , 15-H, 21-H , 6-H, 11-H, 7-H, 9-H), 0.97 (s,
b
b
b
H, 27-H), 0.88 (s, 3H, 26-H), 0.87 (s, 1H, 1-H
a
), 0.82 (s, 3H, 25-H), 0.81 (s, 3H, 24-H), 0.80 (s,
= 213.0 (C-20), 175.3
H, 23-H), 0.79–0.73 (m, 1H, 5-H) ppm; 13C NMR (126 MHz, CDCl3):
δ
(C-28), 171.0 (C-30), 81.0 (C-3), 55.5 (C-17), 55.4 (C-5), 51.3 (C-19), 50.5 (C-9), 50.2 (C-18),
47.6 (C-32), 45.1 (C-35), 42.3 (C-14), 40.8 (C-8), 38.5 (C-1), 38.2 (C-22), 37.9 (C-10), 37.2 (C-4),
36.9 (C-13), 34.3 (C-7), 33.2 (C-16), 30.8 (C-37, C-33), 30.4 (C-29), 29.6 (C-15), 28.7 (C-21),
28.0 (C-23), 27.9 (C-36, C-34), 27.6 (C-12), 23.8 (C-2), 21.4 (C-31), 21.1 (C-11), 18.3 (C-6), 16.6