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8.2 Hz), 3.48 (dd, 1H, J=6.4, 9.7 Hz), 3.53–3.55 (m, 2H),
4.11 (br, 1H), 4.15 (t, 1H, J=4.3 Hz), 4.27 (t, 1H, J=
4.3 Hz), 4.50–4.66 (m, 6H), 7.24–7.33 (m, 15H). 13C NMR
(150 MHz, CDCl3, d): 36.9, 52.7, 69.8, 71.6, 71.7, 72.0,
72.3, 73.2, 73.3, 81.5, 85.6, 127.4 (2), 127.6 (2), 127.72
(2), 127.79 (2), 127.8 (2), 128.3 (2), 128.43 (2),
128.46, 137.8, 138.2, 138.5. HRMS (ESI) calcd for
[C29H33NO4 +H]+, 460.2482; found, 460.2447.
1H, J=3.2, 9.3 Hz), 4.03–4.07 (m, 4H), 4.32 (s, 1H). 13C
NMR (150 MHz, D2O, d): 19.1, 33.2, 34.8, 52.2, 56.0, 62.4,
65.2, 70.6, 73.0, 78.3. HRMS (ESI) calcd for [C10H19NO4 +
H]+, 218.1387; found, 218.1335.
Compounds 20 and 21
To a solution of 3 (0.83 g, 1.1 mmol) in DCM was
added 50% TFA at room temperature. After 5 h, the re-
action was quenched with aqueous NaHCO3 and extract-
ed with DCM. The organic layer was washed with brine,
dried (MgSO4), concentrated, and then purified by CC
(eluent: 3 :1 EtOAc/Hex, silica gel) to give 20 (0.25 g,
0.55 mmol, 48%) and 21 (0.25 g, 0.55 mmol, 48%). Com-
Australine (13)[23]
The reaction was carried out as described above for 4
starting from 12 to give 13 (69 mg, 0.37 mmol, 99%). H
1
NMR (600 MHz, D2O, d): 2.20–2.26 (m, 1H), 2.28–2.33
(m, 1H), 3.35–3.41 (m, 2H), 3.81 (m, 1H), 3.88–3.93 (m,
2H), 3.99 (dd, 1H, J=3.0, 13.2 Hz), 4.15 (dd, 1H, J=7.3,
10.5 Hz), 4.48 (t, 1H, J=7.3 Hz), 4.68 (dd, 1H, J=4.2,
7.3 Hz). 13C NMR (150 MHz, D2O, d): 34.3, 52.2, 55.9,
68.1, 70.6, 71.5, 72.5, 75.4. HRMS (ESI) calcd for
[C8H15NO4 +H]+, 190.1079; found, 190.1020.
1
pound 20. H NMR (600 MHz, CDCl3, d): 1.88 (ddd, 1H,
J=4.4, 10.3, 13.2 Hz), 2.16 (dd, 1H, J=7.1, 13.2 Hz), 3.02
(dd, 1H, J=4.4, 12.1 Hz), 3.23 (td, 1H, J=7.1, 12.1 Hz),
3.52 (d, 1H, J=12.1 Hz), 3.61 (dd, 1H, J=5.0, 9.6 Hz),
3.68 (dd, 1H, J=7.5, 9.6 Hz), 3.89 (t, 1H, J=4.4 Hz),
4.05–4.12 (m, 2H), 4.44–4.63 (m, 7H), 7.20–7.34 (m, 15H).
13C NMR (150 MHz, CDCl3, d): 40.1, 64.1, 67.8, 70.0,
70.3, 72.0, 72.5, 73.1, 73.4, 85.2, 86.6, 127.6, 127.72, 127.79
(2), 127.8, 127.93 (2), 127.99 (2), 128.0, 128.30,
128.38, 128.4, 128.50, 128.54, 137.2, 137.4, 137.8. HRMS
(ESI) calcd for [C29H33NO4 +H]+, 460.2482; found,
Compounds 15 and 16[7a]
The reactions were carried out as described above for 4
and 5 starting from 14 (400 mg, 0.59 mmol) to give 15
(15 mg, 0.076 mmol, 13% over four steps) and 16 (30 mg,
0.15 mmol, 26% over four steps). Compound 15. 1H
NMR (600 MHz, D2O, d): 1.73 (br, 1H), 1.85 (br, 1H),
1.99–2.06 (m, 2H), 3.27 (t, 1H, J=10.8 Hz), 3.48–3.58 (m,
3H), 3.99–4.05 (m, 2H), 4.22 (br, 2H), 4.31 (s, 1H). 13C
NMR (150 MHz, D2O, d): 17.1, 27.7, 48.0, 61.1, 65.8, 68.3,
68.8, 73.3, 75.3. HRMS (ESI) calcd for [C9H17NO4 +H]+,
204.1230; found, 204.1285. Compound 16. 1H NMR
(600 MHz, D2O, d): 1.62–1.66 (m, 1H), 1.86–1.93 (m, 1H),
2.01–2.07 (m, 1H), 2.12–2.17 (m, 1H), 3.33 (td, 1H, J=3.1,
13.5 Hz), 3.42 (br, 1H), 3.48 (dt, 1H, J=4.1, 13.5 Hz), 3.63
(q, 1H, J=4.9 Hz), 3.98 (dd, 1H, J=4.9, 13.5 Hz), 4.04
(dd, 1H, J=3.9, 12.9 Hz), 4.08–4.12 (m, 1H), 4.23 (dd,
1H, J=3.2, 4.9 Hz), 4.40 (br, 1H). 13C NMR (150 MHz,
D2O, d): 17.3, 28.6, 47.6, 57.5, 63.2, 69.7, 70.5, 75.8, 76.9.
HRMS (ESI) calcd for [C9H17NO4 +H]+, 204.1230;
found, 204.1279.
1
460.2459. Compound 21. H NMR (600 MHz, CDCl3, d):
1.80 (ddd, 1H, J=4.2, 9.0, 13.1 Hz), 2.04 (dd, 1H, J=6.9,
13.1 Hz), 2.91 (dd, 1H, J=4.2, 11.5 Hz), 3.00 (td, 1H, J=
6.9, 11.5 Hz), 3.13 (d, 1H, J=11.5 Hz), 3.51 (dd, 1H, J=
3.1, 9.0 Hz), 3.57 (dd, 1H, J=4.9, 9.0 Hz), 3.68–3.71 (m,
1H), 3.83 (t, 1H, J=5.4 Hz), 4.06 (t, 1H, J=5.4 Hz), 4.43–
4.45 (m, 1H), 4.46–4.48 (m, 6H), 7.24–7.33 (m, 15H). 13C
NMR (150 MHz, CDCl3, d): 40.6, 63.6, 66.1, 68.9, 71.9,
72.1, 72.5, 73.2, 74.0, 86.0, 88.7, 127.5 (2), 127.6 (2),
127.70 (2), 127.75 (2), 127.77 (2), 128.34 (2), 128.37
(2), 128.4, 138.0, 138.3, 138.4. HRMS (ESI) calcd for
[C29H33NO4 +H]+, 460.2482; found, 460.2426.
Compound 22
To a solution of 20 (0.12 g, 0.26 mmol) in dry DCM
were added MsCl (0.03 mL, 0.4 mmol) and NEt3
(0.05 mL, 0.4 mmol) at room temperature. After 1 h, the
reaction was quenched with water and extracted with
DCM. The organic layer was washed with brine, dried
(MgSO4), concentrated, and then purified by CC (eluent:
1:1 EtOAc/Hex, silica gel) to give the mesylate (0.13 g,
0.24 mmol, 92%). To a solution of the mesylate (0.06 g,
0.11 mmol) in dry DMF was added NaN3 (0.008 g,
0.12 mmol) at 608. The mixture was stirred at room tem-
perature for 12 h. After quenching the reaction, the or-
ganic layer was washed with brine, dried (MgSO4) and
concentrated. The residue was purified by CC (eluent:
1:1 EtOAc/Hex, silica gel) to give 22 (0.04 g, 0.08 mmol,
Compound 18
The reactions were carried out as described above for
13 starting from 17 (400 mg, 0.59 mmol) to give 18
(30 mg, 0.15 mmol, 25% over four steps). 1H NMR
(600 MHz, D2O, d): 1.92 (br, 1H), 2.12 (br, 3H), 3.45 (d,
1H, J=12.7 Hz), 3.63 (t, 1H, J=11.0 Hz), 3.69 (br, 1H),
3.87 (br, 1H), 3.99 (dd, 1H, J=4.6, 13.0 Hz), 4.07 (dd, 1H,
J=3.3, 13.0 Hz), 4.13 (br, 1H), 4.17 (br, 1H), 4.21 (br,
1H). 13C NMR (150 MHz, D2O, d): 25.5, 28.2, 43.1, 57.3,
60.5, 62.6, 68.5, 76.7, 77.4. HRMS (ESI) calcd for
[C9H17NO4 +H]+, 204.1230; found, 204.1260.
Compound 19
1
The reactions were carried out as described above for
15 starting from 17 (400 mg, 0.59 mmol) to give 19
(28 mg, 0.13 mmol, 27% over four steps). 1H NMR
(600 MHz, D2O, d): 1.75 (br, 1H), 1.93 (br, 3H), 2.24 (dd,
1H, J=4.5, 11.5 Hz), 2.38 (dd, 1H, J=8.1, 11.5 Hz), 3.27
(br, 1H), 3.49 (br, 1H), 3.75 (d, 1H, J=8.1 Hz), 3.97 (dd,
74%). H NMR (600 MHz, CDCl3, d): 1.88–1.92 (m, 1H),
2.03–2.07 (m, 1H), 3.02 (q, 1H, J=6.2 Hz), 3.07 (dd, 1H,
J=5.2, 11.7 Hz), 3.16 (dd, 1H, J=3, 11.64 Hz), 3.53 (t,
1H, J=9.2 Hz), 3.59 (dd, 1H, J=5.1, 9.3 Hz), 3.66 (dd,
1H, J=7.4, 12.4 Hz), 4.05 (t, 1H, J=5.3 Hz), 4.16–4.19
(m, 1H), 4.51–4.69 (m, 6H), 7.27–7.38 (m, 15H).
Isr. J. Chem. 2015, 55, 403 – 411
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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