3.2 Experimental Procedures
43
in H 2 O) (250 ml). After drying over MgSO 4 the solution was concentrated
under reduced pressure. The residue was dried in vacuo to give the target
compound as pale yellow solid (quantitative yield). The obtained product
was used without further purification.
1
H-NMR (600 MHz, CDCl 3 ): δ 4.20–4.16 (m, 1 H, H
12 ), 3.25 (dd, J =
11.6, 4.5 Hz, 1 H, H
3 ), 2.25 (ddd, J = 13.9, 12.1, 3.2 Hz, 1 H, H
11a ), 2.20–2.11
(m, 2 H, H
16a,19a ), 2.05–1.98 (m, 2 H, H
5,19a ), 1.94 (td, J = 13.7, 6.1 Hz, 1 H,
H
15a ), 1.78–1.51 (m, 9 H, H
1a,2ab,6a,7a,11b,18,22ab ), 1.47–1.41 (m, 1 H, H
6b ),
1.39 (s, 3 H, H
27 ), 1.38–1.32 (m, 1 H, H
21a ), 1.32–1.24 (m, 3 H, H
7b,16b,21b ),
1.24–1.17 (m, 4 H, H
15b,26 ), 1.04 (td, J = 13.2, 3.6 Hz, 1 H, H
1b ), 0.99 (s,
6 H, H
23,29 ), 0.90 (s, 3 H, H
30 ), 0.88 (s, 3 H, H
25 ), 0.80–0.76 (m, 4 H, H
5,24 ).
13 C-NMR (150 MHz, CDCl 3 ): δ 179.3 (C
28 ), 91.8 (C
13 ), 78.9 (C
3 ), 65.2
(C
12 ), 55.3 (C
5 ), 52.1 (C
18 ), 45.4 (C
17 ), 44.9 (C
9 ), 43.1 (C
14 ), 42.5 (C
8 ),
39.9 (C
19 ), 39.0 (C
4 ), 38.6 (C
1 ), 36.6 (C
10 ), 34.6 (C
7 ), 34.0 (C
21 ), 33.4
(C
29 ), 32.0 (C
20 ), 29.7 (C
11 ), 29.1 (C
15 ), 28.1 (C
23 ), 27.6 (C
22 ), 27.3 (C
2 ),
23.8 (C
30 ), 21.4 (C
16 ), 20.3 (C
27 ), 19.0 (C
26 ), 17.8 (C
6 ), 16.9 (C
25 ), 15.5
(C
24 ). [α]
20
D
+56.5 (c 1.0, CDCl 3 ). IR (neat) 2932, 2867, 1768, 1713,
1467. HRMS (ESI-TOF) m/z: [M + Na]
+ Calcd for C 30 H 47 ClNaO 3
+
513.3106; Found 513.3106.
3.2.2 12α-Bromo-3β-hydroxyolean-28,13β-olide (26b)
HO
H
H
H
Br
O
O
1
2
3
4
5
6
7
8
9
10
11
12 13
14
15
16
17
18
19
20
21
22
28
24
23
25
26
29
27
30
A round bottom flask, equipped with magnetic stirring bar, was charged
with a solution of oleanolic acid (5) (1.00 mmol, 457 mg, 1.00 equiv) in DCM
(12 ml) and pyridine (15.2 mmol, 1229 μl, 15.2 equiv). After addition of NBS
(1.05 mmol, 187 mg, 1.05 equiv), the reaction was left stirring at 20 °C for
43
in H 2 O) (250 ml). After drying over MgSO 4 the solution was concentrated
under reduced pressure. The residue was dried in vacuo to give the target
compound as pale yellow solid (quantitative yield). The obtained product
was used without further purification.
1
H-NMR (600 MHz, CDCl 3 ): δ 4.20–4.16 (m, 1 H, H
12 ), 3.25 (dd, J =
11.6, 4.5 Hz, 1 H, H
3 ), 2.25 (ddd, J = 13.9, 12.1, 3.2 Hz, 1 H, H
11a ), 2.20–2.11
(m, 2 H, H
16a,19a ), 2.05–1.98 (m, 2 H, H
5,19a ), 1.94 (td, J = 13.7, 6.1 Hz, 1 H,
H
15a ), 1.78–1.51 (m, 9 H, H
1a,2ab,6a,7a,11b,18,22ab ), 1.47–1.41 (m, 1 H, H
6b ),
1.39 (s, 3 H, H
27 ), 1.38–1.32 (m, 1 H, H
21a ), 1.32–1.24 (m, 3 H, H
7b,16b,21b ),
1.24–1.17 (m, 4 H, H
15b,26 ), 1.04 (td, J = 13.2, 3.6 Hz, 1 H, H
1b ), 0.99 (s,
6 H, H
23,29 ), 0.90 (s, 3 H, H
30 ), 0.88 (s, 3 H, H
25 ), 0.80–0.76 (m, 4 H, H
5,24 ).
13 C-NMR (150 MHz, CDCl 3 ): δ 179.3 (C
28 ), 91.8 (C
13 ), 78.9 (C
3 ), 65.2
(C
12 ), 55.3 (C
5 ), 52.1 (C
18 ), 45.4 (C
17 ), 44.9 (C
9 ), 43.1 (C
14 ), 42.5 (C
8 ),
39.9 (C
19 ), 39.0 (C
4 ), 38.6 (C
1 ), 36.6 (C
10 ), 34.6 (C
7 ), 34.0 (C
21 ), 33.4
(C
29 ), 32.0 (C
20 ), 29.7 (C
11 ), 29.1 (C
15 ), 28.1 (C
23 ), 27.6 (C
22 ), 27.3 (C
2 ),
23.8 (C
30 ), 21.4 (C
16 ), 20.3 (C
27 ), 19.0 (C
26 ), 17.8 (C
6 ), 16.9 (C
25 ), 15.5
(C
24 ). [α]
20
D
+56.5 (c 1.0, CDCl 3 ). IR (neat) 2932, 2867, 1768, 1713,
1467. HRMS (ESI-TOF) m/z: [M + Na]
+ Calcd for C 30 H 47 ClNaO 3
+
513.3106; Found 513.3106.
3.2.2 12α-Bromo-3β-hydroxyolean-28,13β-olide (26b)
HO
H
H
H
Br
O
O
1
2
3
4
5
6
7
8
9
10
11
12 13
14
15
16
17
18
19
20
21
22
28
24
23
25
26
29
27
30
A round bottom flask, equipped with magnetic stirring bar, was charged
with a solution of oleanolic acid (5) (1.00 mmol, 457 mg, 1.00 equiv) in DCM
(12 ml) and pyridine (15.2 mmol, 1229 μl, 15.2 equiv). After addition of NBS
(1.05 mmol, 187 mg, 1.05 equiv), the reaction was left stirring at 20 °C for