8438
K. Hattori et al. / Tetrahedron 56 (2000) 8433±8441
over anhydrous magnesium sulfate. After ®ltration, the
solvent was evaporated to afford 9-decenylamine (371 mg,
24%), which was used in the next reaction without further
underAratmosphere. Thereactionmixturewasstirredatroom
temperature for 15 h and quenched with ice water (30 mL).
The organic layer was washed with 5% KHSO4 solution
(30 mL), water (30 mL), 5% Na2CO3 solution (30 mL) and
brine (30 mL), then dried over anhydrous magnesium sulfate.
After ®ltration, the solvent was evaporated to afford a pale
yellow oil that was used in the next reaction without further
puri®cation (2.70 g,crude). 1HNMR (400 MHz):d 1.42±1.55
(m, 4H), 1.74±1.78 (m, 2H), 2.99 (s, 3H), 3.20 (q, J6.4 Hz,
2H), 4.21(t, J6.4 Hz, 2H), 4.82(brs, 1H), 5.09(s, 2H), 7.31±
7.36 (m, 5H).
1
puri®cation. H NMR (400 MHz): d 1.29±1.47 (m, 12H),
2.04 (q, J7.2 Hz, 2H), 2.68 (q, J7.1 Hz, 2H), 4.92±4.97
(m, 2H), 5.01±5.86 (m, 1H); MS (EI) m/z 155 (M1, 30%),
114 (55), 55 (100), 45 (78).
Preparation of 1d was performed analogously to the proce-
dure described for 1a with 9-decenylamine (371 mg,
2.4 mmol). Yield: 82% (567 mg, as a colorless oil); H
1
NMR (400 MHz): d 1.28±1.57 (m, 12H), 2.03 (q,
J7.0 Hz, 2H), 3.18 (q, J6.4 Hz, 2H), 4.72 (brs, 1H),
4.92±5.01 (m, 2H), 5.09 (s, 2H), 5.76±5.86 (m, 1H),
7.31±7.36 (m, 5H); 13C NMR: d 26.56, 28.72, 28.87,
29.07, 29.21, 29.78, 33.62, 40.94, 66.32, 114.03, 127.84,
127.90, 128.30, 136.60, 138.92, 156.28; HRMS (EI) Calcd
for C18H27NO2 (M1) 289.2042. Found 289.2045.
To a solution of the above mesylate (2.70 g, 8.60 mmol) in
anhydrous DMF (10 mL) was added NaN3 (0.84 g,
12.80 mmol). The reaction mixture was stirred at room
temperature for 24 h. The solvent was evaporated and the
residue was partitioned between ethyl acetate (50 mL) and
water (50 mL). The organic layer was washed with water
(50 mL) and brine (50 mL) and dried over anhydrous
magnesium sulfate. The solvent was removed in vacuo,
and ¯ash column chromatography (hexane/ether 5:1)
yielded 1g (1.77 g, 79%) as a colorless oil. 1H NMR
(400 MHz): d 1.39±1.62 (m, 6H), 3.19 (q, J6.6 Hz, 2H),
3.26 (t, J6.6 Hz, 2H), 4.82 (brs, 1H), 5.09 (s, 2H), 7.31±
7.36 (m, 5H); 13C NMR: d 23.82, 28.45, 29.51, 40.79, 51.21,
66.59, 128.06, 128.46, 136.56, 156.37; HRMS (FAB; NBA)
Calcd for C13H19N4O2 (M11H) 263.1508. Found 263.1498.
N-Benzyloxycarbonyl-2-(2-propenyl)cyclopentylamine
(1e). Preparation of 1e was performed analogously to the
procedure described for 1a with 2-(2-propenyl)cyclopentyl-
amine15 (693 mg, 5.50 mmol). Yield: 87% (1.25 g, as a pale
1
yellow oil); H NMR (400 MHz): d 1.24±1.31 (m, 1H),
1.49±2.00 (m, 7H), 2.17±2.22 (m, 1H), 4.08±4.16 (m,
1H), 4.66 (brs, 1H), 4.95±5.02 (m, 2H), 5.09 (s, 2H),
5.70±5.83 (m, 1H), 7.30±7.37 (m, 5H); 13C NMR: d
21.35, 28.98, 32.32, 34.08, 42.42, 54.60, 66.61, 115.41,
128.08, 128.50, 136.58, 137.50, 156.58; HRMS (EI) Calcd
for C16H21NO2 (M1) 259.1572. Found 259.1560.
N-Benzyloxycarbonyl-4-nitrophenethylamine (1h).
A
suspension of 4-nitro phenethylamine hydrochloride
(910 mg, 4.50 mmol) and triethylamine (0.60 mL,
4.40 mmol) in THF (10 mL) was stirred at room tempera-
ture for 1 h. To this suspension was added a solution of N-
(benzyloxycarbonyloxy)succinimide (1.40 g, 5.40 mmol) in
THF (10 mL). The reaction mixture was stirred at room
temperature for 17 h. The solvent was evaporated and the
residue was partitioned between ethyl acetate (50 mL) and
water (50 mL). The organic layer was washed with water
(30 mL), saturated aqueous NaHCO3 solution (30 mL),
water (30 mL) and brine (30 mL), then dried over anhydrous
sodium sulfate. After ®ltration, the solvent was evaporated
to dryness. The residue was recrystallized from EtOH to
1-Benzyloxycarbonyl-trans-4-cinnamylpiperazine (1f).8
Preparation of 1f was performed analogously to the proce-
dure described for 1a with trans-1-cinnamylpiperazine
(3.00 g, 14.80 mmol). Yield: 85% (4.24 g, as a pale yellow
1
oil); H NMR (400 MHz): d 2.23±2.50 (m, 4H), 3.16 (d,
J6.6 Hz, 2H), 3.54 (t, J4.9 Hz, 4H), 5.13 (s, 2H), 6.24
(dt, J6.6 and 15.9 Hz, 1H), 6.52 (d, J15.9 Hz, 1H),
7.21±7.38 (m, 10H); 13C NMR: d 43.8, 52.8, 61.0, 67.1,
126.0, 126.3, 127.6, 127.8, 128.0, 128.4, 133.4, 136.7,
155.2; HRMS (EI) Calcd for C21H24N2O2 (M1) 336.1838.
Found 336.1844.
1
obtain 1h (1.11 g, 82%) as a white solid. Mp 738C; H
1-Azidopentane-5-(N-benzyloxycarbonyl)amine (1g). A
solution of 5-amino-1-pentanol (1.00 g, 10 mmol) and N-
(benzyloxycarbonyloxy)succinimide (2.99 g, 12.00 mmol)
in THF (10 mL) was stirred at room temperature for 19 h.
The solvent was evaporated and the residue was partitioned
between ethyl acetate (50 mL) and water (50 mL). The
organic layer was washed with water (30 mL), saturated
aqueous NaHCO3 solution (30 mL), water (30 mL) and
brine (30 mL), then dried over anhydrous sodium sulfate.
After ®ltration, the solvent was evaporated to afford
NMR (400 MHz): d 2.94 (t, J6.6 Hz, 2H), 3.49 (q,
J6.6 Hz, 1H), 4.81 (brs, 1H), 5.09 (s, 2H), 7.32±7.36
(m, 7H), 8.14 (d, J8.3 Hz, 2H); 13C NMR: d 36.07,
41.69, 66.81, 123.78, 128.13, 128.24, 128.54, 129.63,
136.31, 146.49, 146.79, 156.19; MS (EI) m/z 300 (M1,
8%), 176 (85), 164 (82), 120 (70), 108 (80); Anal. Calcd
for C16H16N2O4: C, 63.99; H, 5.37; N, 9.33. Found: C,
63.80; H, 5.41; N, 9.20.
N-Benzyloxycarbonyl-l-proline benzyl ester (5b).8
A
N-benzyloxycarbonyl-1-hydroxypentyl-5-amine (2.77 g,
crude), which was used in the next reaction without further
suspension of l-proline benzyl ester hydrochloride
(2.42 g, 10.00 mmol) and triethylamine (1.30 mL,
9.30 mmol) in THF (10 mL) was stirred at room tempera-
ture for 1 h. To this suspension was added a solution of N-
(benzyloxycarbonyloxy)succinimide (2.99 g, 12.00 mmol)
in THF (10 mL). The reaction mixture was stirred at room
temperature for 17 h. The solvent was evaporated and the
residue was partitioned between ethyl acetate (50 mL) and
water (50 mL). The organic layer was washed with water
(30 mL), saturated aqueous NaHCO3 solution (30 mL),
1
puri®cation. H NMR (400 MHz): d 1.39±1.58 (m, 6H),
3.20 (q, J6.8 Hz, 2H), 3.60±3.68 (m, 2H), 4.79 (brs,
1H), 5.09 (s, 2H), 7.31±7.36 (m, 5H).
Methanesulfonyl chloride (0.93 mL, 12.00 mmol) was added
dropwise to a cooled (2108C) solution of N-benzyl-
oxycarbonyl-1-hydroxypentyl-5-amine (2.77 g, 11.70 mmol)
and triethylamine (1.70 mL, 12.00 mmol) in CH2Cl2 (20 mL)