3.2 Experimental Procedures
49
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. Subsequently, hydroxylamine hydrochloride (3.2 mmol, 222 mg, 3.2 equiv) was added, and the reaction was
left stirring at 20 °C for 21 h. Afterwards, the solution was diluted with
DCM (12 ml), filtered over a glass frit (P 16) and the residue was washed
with DCM (2 × 4 ml). The organics were 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 (0.99 mmol, 555 mg, 99 %). The obtained product was used without
further purification. In a 20 mmol scale the target compound was obtained
in 97 % yield. The spectroscopic data is in accordance with the literature.
[5]
1
H-NMR (600 MHz, CDCl 3 ): δ 7.83 (s, 1 H, H
3-NOH ), 4.30 (t, J =
2.9 Hz, 1 H, H
12 ), 2.97 (ddd, J = 15.5, 6.1, 4.1 Hz, 1 H, H
2a ), 2.44–2.29 (m,
3 H, H
2b,11a,19a ), 2.16 (td, J = 13.4, 5.7 Hz, 1 H, H
16a ), 2.05–1.92 (m, 3 H,
H
15a,18,19b ), 1.84 (d, J = 15.2 Hz, 1 H, H
11b ), 1.82–1.77 (m, 2 H, H
1a,9 ),
1.64 (dd, J = 9.3, 3.5 Hz, 2 H, H
22ab ), 1.61–1.44 (m, 3 H, H
6ab,7a ), 1.43 (s,
3 H, H
27 ), 1.39–1.31 (m, 2 H, H
21ab ), 1.31–1.19 (m, 7 H, H
1b,7b,15b,16b,26 ),
1.19–1.14 (m, 4 H, H
5,23 ), 1.06 (s, 3 H, H
24 ), 0.99 (s, 3 H, H
29 ), 0.98 (s, 3 H,
H
25 ), 0.90 (s, 3 H, H
30 ).
13 C-NMR (150 MHz, CDCl 3 ): δ 179.0 (C
28 ),
167.1 (C
3 ), 91.8 (C
13 ), 56.4 (C
12 ), 55.4 (C
5 ), 52.5 (C
18 ), 45.7 (C
17 ), 45.3
(C
9 ), 43.6 (C
14 ), 42.5 (C
8 ), 40.4 (C
4 ), 40.1 (C
19 ), 38.4 (C
1 ), 36.7 (C
10 ), 34.3
(C
7 ), 34.0 (C
21 ), 33.4 (C
29 ), 32.0 (C
20 ), 30.8 (C
11 ), 29.3 (C
15 ), 27.6 (C
22 ),
27.6 (C
23 ), 23.7 (C
30 ), 22.9 (C
24 ), 21.4 (C
16 ), 21.1 (C
27 ), 19.0 (C
26 ), 18.6
(C
6 ), 16.9 (C
2 ), 16.9 (C
25 ). [α]
20
D +35.5 (c 1.0, CDCl 3 ). IR (neat) 3280,
2956, 2932, 2868, 1775, 1465. HRMS (ESI-TOF) m/z: [M + Na]
+ Calcd
for C 30 H 46 BrNNaO 3
+ 570.2553; Found 570.2550.
49
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. Subsequently, hydroxylamine hydrochloride (3.2 mmol, 222 mg, 3.2 equiv) was added, and the reaction was
left stirring at 20 °C for 21 h. Afterwards, the solution was diluted with
DCM (12 ml), filtered over a glass frit (P 16) and the residue was washed
with DCM (2 × 4 ml). The organics were 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 (0.99 mmol, 555 mg, 99 %). The obtained product was used without
further purification. In a 20 mmol scale the target compound was obtained
in 97 % yield. The spectroscopic data is in accordance with the literature.
[5]
1
H-NMR (600 MHz, CDCl 3 ): δ 7.83 (s, 1 H, H
3-NOH ), 4.30 (t, J =
2.9 Hz, 1 H, H
12 ), 2.97 (ddd, J = 15.5, 6.1, 4.1 Hz, 1 H, H
2a ), 2.44–2.29 (m,
3 H, H
2b,11a,19a ), 2.16 (td, J = 13.4, 5.7 Hz, 1 H, H
16a ), 2.05–1.92 (m, 3 H,
H
15a,18,19b ), 1.84 (d, J = 15.2 Hz, 1 H, H
11b ), 1.82–1.77 (m, 2 H, H
1a,9 ),
1.64 (dd, J = 9.3, 3.5 Hz, 2 H, H
22ab ), 1.61–1.44 (m, 3 H, H
6ab,7a ), 1.43 (s,
3 H, H
27 ), 1.39–1.31 (m, 2 H, H
21ab ), 1.31–1.19 (m, 7 H, H
1b,7b,15b,16b,26 ),
1.19–1.14 (m, 4 H, H
5,23 ), 1.06 (s, 3 H, H
24 ), 0.99 (s, 3 H, H
29 ), 0.98 (s, 3 H,
H
25 ), 0.90 (s, 3 H, H
30 ).
13 C-NMR (150 MHz, CDCl 3 ): δ 179.0 (C
28 ),
167.1 (C
3 ), 91.8 (C
13 ), 56.4 (C
12 ), 55.4 (C
5 ), 52.5 (C
18 ), 45.7 (C
17 ), 45.3
(C
9 ), 43.6 (C
14 ), 42.5 (C
8 ), 40.4 (C
4 ), 40.1 (C
19 ), 38.4 (C
1 ), 36.7 (C
10 ), 34.3
(C
7 ), 34.0 (C
21 ), 33.4 (C
29 ), 32.0 (C
20 ), 30.8 (C
11 ), 29.3 (C
15 ), 27.6 (C
22 ),
27.6 (C
23 ), 23.7 (C
30 ), 22.9 (C
24 ), 21.4 (C
16 ), 21.1 (C
27 ), 19.0 (C
26 ), 18.6
(C
6 ), 16.9 (C
2 ), 16.9 (C
25 ). [α]
20
D +35.5 (c 1.0, CDCl 3 ). IR (neat) 3280,
2956, 2932, 2868, 1775, 1465. HRMS (ESI-TOF) m/z: [M + Na]
+ Calcd
for C 30 H 46 BrNNaO 3
+ 570.2553; Found 570.2550.