1048
S. Honzawa et al. / Tetrahedron: Asymmetry 13 (2002) 1043–1052
414.2307. Found: 414.2307. IR (KBr) 3500–3200, 1702
J=8 Hz), 7.72 (1H, s), 7.84 (1H, s), 7.87 (1H, s), 8.04
(1H, d, J=8 Hz), 8.15 (2H, d, J=8 Hz), 8.24 (1H, s),
8.28 (1H, d, J=8 Hz). 13C NMR (CDCl3) l 23.3, 23.5,
23.6, 23.6, 28.6, 43.0, 51.4, 51.8, 79.6, 108.9, 118.1,
120.5, 120.9, 121.2, 122.6, 124.3, 124.9, 125.1, 125.2,
125.7, 125.9, 127.2, 127.3, 128.0, 128.1, 128.2, 128.6,
129.7, 129.8, 130.1, 130.2, 130.6, 130.9, 131.1, 131.2,
131.7, 132.3, 132.7, 133.0, 134.5, 136.1, 136.7, 136.9,
137.3, 155.5.
1
cm−1. H NMR (CDCl3) l 1.50 (9H, s), 1.93 (6H, s),
4.42 (1H, d, J=15 Hz), 4.50 (1H, d, J=14 Hz), 4.85
(1H, dd, J=5,14 Hz), 4.97 (1H, dd, J=6,14 Hz), 5.03
(1H, br), 7.39 (2H, d, J=7 Hz), 7.59 (1H, t, J=8 Hz),
7.59 (1H, t, J=8 Hz), 7.71 (1H, s), 7.74 (1H, s), 8.04
(1H, d, J=8 Hz), 8.06 (1H, d, J=8 Hz). 13C NMR
(CDCl3) l 23.6, 23.6, 28.6, 43.0, 44.1, 79.5, 120.2, 120.5,
123.1, 124.8, 125.0, 125.8, 128.0, 128.1, 130.2, 130.3,
131.5, 131.6, 131.7, 133.0, 136.7, 136.8, 137.8, 155.6.
(P)-isomer: [h]2D6 −90 (c 1.0, CHCl3).
4.6. (M,M)-5-{8-(t-Butoxycarbonylaminomethyl)-1,12-
dimethylbenzo[c]phenanthrene-5-yl}methylaminomethyl-
8-(t-butoxycarbonylaminomethyl)-1,12-dimethylbenzo[c]-
phenanthrene, (M,M)-8
4.5. (M,M)-5-{8-(t-Butoxycarbonylaminomethyl)-1,12-
dimethylbenzo[c]phenanthrene-5-yl}methylaminomethyl-
8-cyano-1,12-dimethylbenzo[c]phenanthrene, (M,M)-7
Under an argon atmosphere, to a solution of (M,M)-7
(90 mg, 0.13 mmol) in dichloromethane (20 mL) was
added 1.0 M diisobutylaluminum hydride in hexane
(1.0 mL, 1.0 mmol) at 0°C and the mixture was stirred
for 30 min at the temperature. Then the mixture was
added to a suspension of sodium borohydride (200 mg,
5.4 mmol) in tetrahydrofuran (10 mL) and methanol
(20 mL) at 0°C. The ice bath was removed and stirring
was continued at room temperature for 30 min, when
saturated aqueous ammonium chloride was added.
After being stirred for 30 min at room temperature,
aqueous 10% sodium hydroxide was added. The
organic materials were extracted with dichloromethane
three times. The combined organic layers were washed
with water and brine, dried over potassium carbonate,
and concentrated in vacuo. The resulted amorphous
solid was diluted with dichloromethane (10 mL), to
which di(t-butyl) dicarbonate (2 g, 10 mmol), water (5
mL), and aqueous 10% sodium hydroxide (5 mL) were
added successively. The mixture was stirred for 30 min
at room temperature, and the reaction was quenched by
adding saturated aqueous ammonium chloride. The
organic materials were extracted with ethyl acetate
three times. The combined organic layers were washed
with water and brine, dried over magnesium sulfate,
and concentrated in vacuo. Purification by silica gel
chromatography (ethyl acetate/hexane=1/2) gave
(M,M)-8 (80 mg, 70%). Mp 180°C dec. (ethyl acetate/
hexane). [h]2D7 −8.2 (c 2.0, CHCl3). Anal. calcd for
C59H65N3O6: C, 77.69; H, 7.18; N, 4.61. Found: C,
78.06; H, 7.12; N, 4.25%. MS (FAB, NBA) m/z 911
(M+). IR (KBr) 3500–3300, 1696 cm−1. 1H NMR
(CDCl3 at 50°C) l 1.48 (18H, s), 1.60 (9H, s), 1.87 (6H,
s), 1.91 (6H, s), 4.57 (2H, d, J=14 Hz), 4.65 (2H, brs),
4.79 (2H, dd, J=5, 14 Hz), 4.85 (2H, d, J=14 Hz), 5.33
(2H, brs), 7.09 (2H, s), 7.14 (2H, s), 7.35 (2H, d, J=7
Hz), 7.40 (2H, d, J=7 Hz), 7.49 (2H, t, J=7 Hz), 7.59
(2H, t, J=8 Hz), 7.98 (2H, d, J=8 Hz), 8.00 (2H, brs).
13C NMR (CDCl3 at 50°C) l 23.5, 23.5, 28.6, 28.7,
42.8, 48.1, 79.5, 80.5, 120.4, 124.0, 124.9, 125.8, 127.4,
127.7, 127.9, 128.0, 128.1, 130.3, 130.5, 131.1, 131.6,
131.7, 132.1, 132.9, 136.6, 136.7, 155.5, 155.8. (P,P)-8:
[h]2D8 +8.3 (c 1.6, CHCl3). (P,M)-8: Mp 180°C dec.
A solution of (M)-monoamine obtained as above (150
mg, 0.36 mmol) and (M)-6 (120 mg, 0.4 mmol) in
toluene (10 mL) was heated under reflux for 24 h. The
mixture was added to a suspension of sodium borohy-
dride (300 mg, 8 mmol) in methanol (20 mL) and
tetrahydrofuran (10 mL) at 0°C. The mixture was
stirred at the temperature for 10 min, and the reaction
was quenched by adding saturated aqueous ammonium
chloride. The organic materials were extracted with
ethyl acetate three times. The combined organic layers
were washed with water and brine, dried over magne-
sium sulfate, and concentrated in vacuo. Purification by
silica gel chromatography (ethyl acetate/hexane=1/2)
gave (M,M)-7 (180 mg, 70%). Mp 150°C dec. (ethyl
acetate/hexane). [h]D27 −14 (c 1.2, CHCl3). Anal. calcd
for C49H45N3O2: C, 83.14; H, 6.41; N, 5.94. Found: C,
82.98; H, 6.09; N, 5.57%. LRMS (EI, 70 eV) m/z 707
(M+, 1%), 607 (M+−Boc, 5%), 299 (MeAr*CH2NH2,
100%). IR (KBr) 3500–3300, 2222, 1704 cm−1. 1H NMR
(CDCl3) l 1.50 (9H, s), 1.89 (3H, s), 1.92 (3H, s), 1.93
(6H, s), 4.49 (1H, d, J=14 Hz), 4.49 (1H, d, J=14 Hz),
4.59 (1H, d, J=15 Hz), 4.63 (1H, d, J=13 Hz), 4.81–
5.00 (3H, m), 7.39 (1H, d, J=7 Hz), 7.41 (1H, d, J=7
Hz), 7.42 (1H, d, J=8 Hz), 7.49 (1H, d, J=7 Hz), 7.53
(1H, dd, J=7, 8 Hz), 7.59 (1H, dd, J=7, 8 Hz), 7.60
(1H, dd, J=7, 8 Hz), 7.70 (1H, t, J=8 Hz), 7.71 (1H,
s), 7.83 (1H, s), 7.86 (1H, s), 8.04 (1H, d, J=8 Hz), 8.14
(2H, d, J=8 Hz), 8.23 (1H, s), 8.28 (1H, d, J=8 Hz).
13C NMR (CDCl3) l 23.3, 23.5, 23.6, 23.6, 28.6, 43.0,
51.4, 51.8, 79.6, 109.0, 118.1, 120.6, 120.9, 121.2, 122.6,
124.3, 124.9, 125.2, 125.3, 125.7, 125.9, 127.2, 127.3,
128.0, 128.1, 128.2, 128.6, 129.7, 129.8, 130.1, 130.3,
130.6, 130.9, 131.1, 131.2, 131.7, 132.3, 132.7, 133.0,
134.6, 136.2, 136.7, 136.9, 137.3, 155.5. (P,P)-7: [h]D26
+13 (c 1.0, CHCl3). (P,M)-7 was obtained from (P)-5
and (M)-6 in 82% yield. Mp 150°C dec. (ethyl acetate/
hexane). [h]2D6 −52 (c 0.6, CHCl3). Anal. calcd for
C49H45N3O2: C, 83.14; H, 6.41; N, 5.94. Found: C,
83.41; H, 5.89; N, 6.07%. LRMS (EI, 70 eV) m/z 707
(M+, 3%), 607 (M+−Boc, 19%), 310 (NC-Ar*CH2NH2,
100%). IR (KBr) 3500–3300, 2222, 1705 cm−1. 1H NMR
(CDCl3) l 1.50 (9H, s), 1.90 (3H, s), 1.91 (3H, s), 1.93
(6H, s), 4.48 (1H, d, J=14 Hz), 4.49 (1H, d, J=14 Hz),
4.61 (1H, d, J=15 Hz), 4.65 (1H, d, J=14 Hz), 4.80–
5.00 (3H, m), 7.39 (1H, d, J=7 Hz), 7.41 (1H, d, J=7
Hz), 7.43 (1H, d, J=8 Hz), 7.49 (1H, d, J=7 Hz), 7.54
(1H, t, J=8 Hz), 7.60 (2H, t, J=8 Hz), 7.70 (1H, t,
(ethyl
acetate/hexane).
Anal.
calcd
for
C59H65N3O6·H2O: C, 76.18; H, 7.26; N, 4.52. Found: C,
76.41; H, 7.02; N, 4.18%. MS (FAB, NBA) m/z 911
(M+). IR (KBr) 3500–3300, 1697 cm−1. 1H NMR