44
3 Experimental Section
60 min. Then i-PrOH (1.60 mmol, 122 μl, 1.60 equiv) was added, and the
mixture was left stirring at 20 °C for 30 min. The solution was subsequently
diluted with DCM (20 ml) and washed with HCl solution (1 m in H 2 O)
(32 ml). The aqueous phase was extracted with DCM (2 × 16 ml). The
combined organic layers were washed with NaOH solution (1 m in H 2 O)
(32 ml), followed by NH 4 Cl solution (half-saturated in H 2 O) (16 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. The spectroscopic data is in accordance with the literature.
[36,62]
1 H-NMR (600 MHz, CDCl 3 ): δ 4.30 (dd, J = 3.6, 2.4 Hz, 1 H, H
12 ),
3.26 (dd, J = 11.6, 4.4 Hz, 1 H, H
3 ), 2.40–2.31 (m, 2 H, H
11a,19a ), 2.16
(td, J = 13.4, 5.7 Hz, 1 H, H
16a ), 2.04–1.92 (m, 3 H, H
15a,18,19a ), 1.85 (dt,
J = 15.0, 2.3 Hz, 1 H, H
11b ), 1.77–1.73 (m, 1 H, H
9 ), 1.72–1.60 (m, 5 H,
H
1a,2ab,22ab ), 1.60–1.51 (m, 2 H, H
6a,7a ), 1.47–1.40 (m, 4 H, H
6b,27 ), 1.40–
1.24 (m, 4 H, H
7b,16a,21ab ), 1.23–1.17 (m, 4 H, H
15b,26 ), 1.11–1.04 (m, 1 H,
H
1b ), 1.00 (s, 6 H, H
23,29 ), 0.90 (s, 3 H, H
30 ), 0.88 (s, 3 H, H
25 ), 0.79 (dd,
J = 12.1, 1.7 Hz, 1 H, H
5 ), 0.77 (s, 3 H, H
24 ).
13 C-NMR (150 MHz,
CDCl 3 ): δ 179.1 (C
28 ), 91.8 (C
13 ), 78.8 (C
3 ), 56.6 (C
12 ), 55.3 (C
5 ), 52.5
(C
18 ), 45.7 (C
9 ), 45.5 (C
17 ), 43.5 (C
14 ), 42.5 (C
8 ), 40.1 (C
19 ), 39.0 (C
4 ),
38.4 (C
1 ), 36.7 (C
10 ), 34.7 (C
7 ), 34.0 (C
21 ), 33.4 (C
29 ), 32.0 (C
20 ), 30.6
(C
11 ), 29.3 (C
15 ), 28.1 (C
23 ), 27.6 (C
22 ), 27.3 (C
2 ), 23.7 (C
30 ), 21.4 (C
16 ),
21.3 (C
27 ), 19.2 (C
26 ), 17.8 (C
6 ), 17.1 (C
25 ), 15.5 (C
24 ). [α]
20
D +66.6 (c 1.0,
CDCl 3 ). HRMS (ESI-TOF) m/z: [M + Na]
+ Calcd for C 30 H 47 BrNaO 3
+
557.2601; Found 557.2591.
3 Experimental Section
60 min. Then i-PrOH (1.60 mmol, 122 μl, 1.60 equiv) was added, and the
mixture was left stirring at 20 °C for 30 min. The solution was subsequently
diluted with DCM (20 ml) and washed with HCl solution (1 m in H 2 O)
(32 ml). The aqueous phase was extracted with DCM (2 × 16 ml). The
combined organic layers were washed with NaOH solution (1 m in H 2 O)
(32 ml), followed by NH 4 Cl solution (half-saturated in H 2 O) (16 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. The spectroscopic data is in accordance with the literature.
[36,62]
1 H-NMR (600 MHz, CDCl 3 ): δ 4.30 (dd, J = 3.6, 2.4 Hz, 1 H, H
12 ),
3.26 (dd, J = 11.6, 4.4 Hz, 1 H, H
3 ), 2.40–2.31 (m, 2 H, H
11a,19a ), 2.16
(td, J = 13.4, 5.7 Hz, 1 H, H
16a ), 2.04–1.92 (m, 3 H, H
15a,18,19a ), 1.85 (dt,
J = 15.0, 2.3 Hz, 1 H, H
11b ), 1.77–1.73 (m, 1 H, H
9 ), 1.72–1.60 (m, 5 H,
H
1a,2ab,22ab ), 1.60–1.51 (m, 2 H, H
6a,7a ), 1.47–1.40 (m, 4 H, H
6b,27 ), 1.40–
1.24 (m, 4 H, H
7b,16a,21ab ), 1.23–1.17 (m, 4 H, H
15b,26 ), 1.11–1.04 (m, 1 H,
H
1b ), 1.00 (s, 6 H, H
23,29 ), 0.90 (s, 3 H, H
30 ), 0.88 (s, 3 H, H
25 ), 0.79 (dd,
J = 12.1, 1.7 Hz, 1 H, H
5 ), 0.77 (s, 3 H, H
24 ).
13 C-NMR (150 MHz,
CDCl 3 ): δ 179.1 (C
28 ), 91.8 (C
13 ), 78.8 (C
3 ), 56.6 (C
12 ), 55.3 (C
5 ), 52.5
(C
18 ), 45.7 (C
9 ), 45.5 (C
17 ), 43.5 (C
14 ), 42.5 (C
8 ), 40.1 (C
19 ), 39.0 (C
4 ),
38.4 (C
1 ), 36.7 (C
10 ), 34.7 (C
7 ), 34.0 (C
21 ), 33.4 (C
29 ), 32.0 (C
20 ), 30.6
(C
11 ), 29.3 (C
15 ), 28.1 (C
23 ), 27.6 (C
22 ), 27.3 (C
2 ), 23.7 (C
30 ), 21.4 (C
16 ),
21.3 (C
27 ), 19.2 (C
26 ), 17.8 (C
6 ), 17.1 (C
25 ), 15.5 (C
24 ). [α]
20
D +66.6 (c 1.0,
CDCl 3 ). HRMS (ESI-TOF) m/z: [M + Na]
+ Calcd for C 30 H 47 BrNaO 3
+
557.2601; Found 557.2591.