794
T. Kumamoto et al. / Tetrahedron: Asymmetry 12 (2001) 791–795
2.96 (1H, dd, J=4.8, 4.8 Hz, 3%-H), 3.48 (1H, m, 2%-H),
4.11 (1H, dd, J=11.0, 5.2 Hz, 1%-H), 4.35 (1H, dd,
J=11.0, 3.2 Hz, 1%-H), 5.21 (2H, s, PhCH2O), 6.71 (1H,
d, J=8.6 Hz, 2- or 3-H), 6.76 (1H, d, J=8.6 Hz, 2- or
3-H), 7.35 (1H, dd, J=7.6, 7.2 Hz, 4%%-H), 7.41 (2H, dd,
J=8.4, 6.4 Hz, 3%%-, 5%%-H), 7.50–7.55 (4H, m, 6-, 7-, 2%%-,
6%%-H), 8.24–8.28 (1H, m, 5- or 8-H), 8.28–8.32 (1H, m,
5- or 8-H). HRFABMS m/z: 306.1253 (calcd for
C20H18O3: 306.1256).
and purification gave (R)-10 as yellow prisms (656 mg,
1
76%), mp 103–104°C. IR wmax: 3273 cm−1. H NMR
(400 MHz) l 1.13 (6H, d, J=6.1 Hz, CHMe2), 2.86
(1H, dd, J=12.0, 7.6 Hz, 1-H), 2.90 (1H, m,
NHCHMe2), 3.02 (1H, br d, J=12.0 Hz, 1-H), 4.09
(1H, dd, J=9.5, 5.2 Hz, 3-H), 4.15 (1H, dd, J=9.2, 4.9
Hz, 3-H), 4.19 (1H, m, 2-H), 5.20 (2H, s, PhCH2O),
6.71 (1H, d, J=8.2 Hz, 2%- or 3%-H), 6.76 (1H, d, J=8.2
Hz, 2%- or 3%-H), 7.35 (1H, dd, J=7.3, 7.3 Hz, 4%%-H),
7.41 (2H, dd, J=7.3, 7.3 Hz, 3%%-, 5%%-H), 7.49-7.53 (4H,
m, 6%-, 7%-, 2%%-, 6%%-H), 8.19–8.22 (1H, m, 5%- or 8%-H),
8.28–8.32 (1H, m, 5%- or 8%-H). Anal. calcd for
C23H27NO3: C, 75.58; H, 7.45; N, 3.83. Found: C,
75.49; H, 7.48; N, 3.65%.
4.9. Preparation of (S)-(+)-1-benzyloxy-4-oxiranyl-
methoxynaphthalene (S)-(+)-9
A mixture of a crude 7 (856 mg, 3.42 mmol) and CsF
(1.62 g,10.7 mmol) in DMF (5 mL) and a solution of
(S)-8 (870 mg, 3.36 mmol) in DMF (5 mL) were
reacted under the same conditions described for ( )-9
4.12. Preparation of (S)-3-(4-benzyloxy-1-naphthoxy)-1-
isopropylamino-2-propanol (S)-10
above. Work-up and purification gave (S)-9 as colorless
24
589
prisms (557 mg, 61%, 97% ee), mp 81–82°C. [h]
1
+7.8 2.0 (c=0.20, CHCl3). H NMR (500 MHz) l 2.84
A mixture of (S)-9 (567 mg, 1.85 mmol), K2CO3 (1.27
g, 9.25 mmol) and isopropylamine (3.8 mL, 44.4 mmol)
in DMF (4 mL) was heated at 50°C for 18 h. Work-up
and purification gave (S)-10 as yellow prisms (516 mg,
(1H, dd, J=4.9, 2.4 Hz, 3%-H), 2.96 (1H, dd, J=4.9, 4.3
Hz, 3%-H), 3.46–3.50 (1H, m, 2%-H), 4.11 (1H, dd,
J=11.2, 5.5 Hz, 1%-H), 4.35 (1H, dd, J=11.2, 3.4 Hz,
1%-H), 5.20 (2H, s, PhCH2O), 6.71 (1H, d, J=8.4 Hz, 2-
or 3-H), 6.76 (1H, d, J=8.4 Hz, 2- or 3-H), 7.34–7.36
(1H, m, 4%%-H), 7.41–7.44 (2H, m, 3%%-, 5%%-H), 7.50–7.55
(4H, m, 6-, 7-, 2%%-, 6%%-H), 8.24–8.27 (1H, m, 5- or 8-H),
8.28–8.32 (1H, m, 5- or 8-H). HRFABMS m/z:
306.1253 (calcd for C20H18O3: 306.1256).
1
76%), mp 103–104°C. IR wmax: 3272 cm−1. H NMR
(400 MHz) l 1.14 (6H, d, J=5.8 Hz, CHMe2), 2.86
(1H, dd, J=11.9, 7.6 Hz, 1-H), 2.91 (1H, m,
NHCHMe2), 3.02–3.05 (1H, m, 1-H), 4.08 (1H, dd,
J=9.5, 4.9 Hz, 3-H), 4.15 (1H, dd, J=8.9, 4.9 Hz,
3-H), 4.21 (1H, m, 2-H), 5.20 (2H, s, PhCH2O), 6.70
(1H, d, J=8.2 Hz, 2%- or 3%-H), 6.75 (1H, d, J=8.2 Hz,
2%- or 3%-H), 7.34 (1H, dd, J=7.3, 7.3 Hz, 4%%-H), 7.41
(2H, dd, J=7.3, 7.3 Hz, 3%%-, 5%%-H), 7.50-7.53 (4H, m,
6%-, 7%-, 2%%-, 6%%-H), 8.19–8.21 (1H, m, 5%- or 8%-H),
8.29–8.31 (1H, m, 5%- or 8%-H). Anal. calcd for
C23H27NO3: C, 75.58; H, 7.45; N, 3.83. Found: C,
75.75; H, 7.47; N, 3.71%.
4.10. Preparation of ( )-3-(4-benzyloxy-1-naphthoxy)-1-
isopropylamino-2-propanol ( )-10
A mixture of ( )-9 (189 mg, 0.62 mmol), K2CO3 (479
mg, 3.47 mmol) and iso-propylamine (1.4 mL, 16.4
mmol) in DMF (2 mL) was heated at 50°C for 15 h.
After further addition of iso-propylamine (1.4 mL, 16.4
mmol), the mixture was heated at 50°C for 6 h. After
excess iso-propylamine was evaporated, H2O (100 mL)
was added and the mixture extracted with AcOEt (3×
100 mL). The combined organic layer was washed with
H2O (5×100 mL) and brine (120 mL) and evaporated.
Recrystallization of the residue from benzene gave ( )-
10 as yellow prisms (209 mg, 93%), mp 107–109°C. IR
4.13. Preparation of ( )-4-OHPL hydrochloride ( )-
2·HCl
A 3.3% solution of HCl gas in Et2O (3 mL) was added
to a solution of ( )-10 (50 mg, 0.14 mmol) in Et2O (20
mL) under ice-cooling and then the solvent was evapo-
rated to give ( )-10·HCl as colorless prisms (106 mg),
mp 172–173°C. A suspension of 20% Pd(OH)2 on C (26
mg) in EtOH (1 mL) was stirred at rt and atmospheric
pressure for 20 min under H2. A solution of ( )-10·HCl
in EtOH (2.5 mL) was added and the mixture was then
stirred under the same conditions for 1.5 h and diluted
with EtOH (30 mL). The catalyst was filtered off
through a Celite pad and the filtrate was evaporated.
The residue was washed with AcOEt and Et2O to give
( )-2·HCl as pale brown prisms (168 mg, 61%), mp
1
wmax: 3271 cm−1. H NMR (400 MHz) l 1.17 (6H, d,
J=5.5 Hz, CHMe2), 2.86–2.91 (1H, m, NHCHMe2),
2.96 (1H, m, 1-H), 3.06 (1H, m, 1-H), 4.08 (1H, dd,
J=9.2, 5.2 Hz, 3-H), 4.15 (1H, dd, J=9.2, 5.2 Hz,
3-H), 4.29 (1H, m, 2-H), 5.19 (2H, s, PhCH2O), 6.68
(1H, d, J=8.2 Hz, 2%- or 3%-H), 6.74 (1H, d, J=8.2 Hz,
2%- or 3%-H), 7.34 (1H, dd, J=9.4, 9.4 Hz, 4%%-H), 7.41
(2H, dd, J=9.4, 9.4 Hz, 3%%-, 5%%-H), 7.50–7.52 (4H, m,
6%-, 7%-, 2%%-, 6%%-H), 8.18–8.21 (1H, m, 5%- or 8%-H),
8.28–8.31 (1H, m, 5%- or 8%-H). Anal. calcd for
C23H27NO3: C, 75.58; H, 7.45; N, 3.83. Found: C,
75.51; H, 7.48; N, 3.78%.
1
165–167°C. IR wmax: 3193 cm−1. H NMR (400 MHz,
CD3OD) l 1.36 (6H, dd, J=7.0, 7.0 Hz, CHMe2), 3.20
(1H, dd, J=12.5, 9.8 Hz, 1-H), 3.34 (1H, dd, J=12.5,
2.8 Hz, 1-H), 3.45 (1H, dq, J=6.4, 6.4 Hz, NCHMe2),
4.08 (1H, dd, J=10.1, 6.8 Hz, 3-H), 4.15 (1H, dd,
J=10.1, 5.0 Hz, 3-H), 4.37 (1H, m, 2-H), 6.73 (1H, d,
J=8.2 Hz, 2%- or 3%-H), 6.76 (1H, d, J=8.2 Hz, 2%- or
3%-H), 7.42–7.47 (2H, m, 6%-, 7%-H), 8.12–8.15 (1H, m, 5%-
or 8%-H), 8.18–8.20 (1H, m, 5%- or 8%-H).
4.11. Preparation of (R)-3-(4-benzyloxy-1-naphthoxy)-
1-isopropylamino-2-propanol (R)-10
A mixture of (R)-9 (705 mg, 2.30 mmol), K2CO3 (1.59
g, 11.5 mmol) and isopropylamine (4.7 mL, 55.2 mmol)
in DMF (5 mL) was heated at 50°C for 14 h. Work-up