9508 J . Org. Chem., Vol. 63, No. 25, 1998
Okubo et al.
× 104). IR (KBr) 3234, 1655 cm-1. IR (CHCl3, 34.7 mM) 3374,
mmHg for 1 day. MS (FAB, NBA) m/z 2634 (M+ + 2). UV-
vis (CHCl3) λmax (ꢀ) 306 nm (1.1 × 105). IR (KBr) 2930, 2860,
3186, 1651 cm-1
. HRMS (EI, 70 eV) calcd for C22H20O2:
630.3247. Found: 630.3246. 1H NMR (600 MHz, CDCl3, 32
mM) δ 1.45-1.63 (6 H, m), 1.80 (6 H, s), 1.91 (6 H, s), 2.06 (6
H, s), 2.24-2.39 (4 H, m), 6.37 (2 H, s), 6.78 (2 H, s), 6.98 (2
H, s), 7.41 (2 H, d, J ) 7.0 Hz), 7.64 (2 H, dd, J ) 7.0, 8.2 Hz),
7.73 (2 H, s), 8.51 (2 H, d, J ) 8.2 Hz). 13C NMR (150 MHz,
CDCl3, 32 mM) δ 18.6, 19.1, 22.8, 23.3, 26.3, 33.0, 45.1, 123.5,
124.6, 124.9, 125.9, 126.9, 127.3, 127.6, 128.6, 128.9, 129.9,
131.0, 132.5, 134.4, 136.8, 170.0. A similar treatment of (P)-1
gave (P)-8 (30%), which was accompanied by (P,P)-9 (14%).
Mp >300 °C (benzene-MeOH). [R]D26 -32.2 (c 0.534, CHCl3).
1647 cm-1
.
(P )-N,N′-Diben zyl[1+1]cycloa m id e. Under an argon at-
mosphere, to an ice cooled solution of (P)-8 (7.5 mg, 0.012
mmol) in THF (2 mL) were added NaH (60% oil suspension,
1.5 mg, 0.038 mmol) and benzyl bromide (5.7 µL, 0.048 mmol)
successively. The mixture was vigorously stirred for 23 h at
room temperature and was added to 2 M hydrochloric acid.
The organic materials were extracted with chloroform, and the
extracts were washed with water and brine. After the solution
was dried over MgSO4, the solvents were removed in vacuo,
and the crude product was purified by silica gel chromatog-
raphy (n-hexane-ethyl acetate) giving the product (9.7 mg,
(P )-N,N′-Dim eth yl[1+1]cycloa m id e. Under an argon
atmosphere, to an ice cooled solution of (P)-8 (7.5 mg, 0.012
mmol) in tetrahydrofuran (2 mL) was added NaH (60% oil
suspension, 1.5 mg, 0.038 mmol) and methyl iodide (3.0 µL,
0.048 mmol) successively. The mixture was vigorously stirred
for 23 h at room temperature and was added to 2 M hydro-
chloric acid. The organic materials were extracted with
chloroform, and the extracts were washed with water and
brine. After the solution was dried over MgSO4, the solvents
were removed in vacuo, and the crude product was purified
by silica gel chromatography (n-hexane-ethyl acetate) giving
the product (7.8 mg, 100%). Mp >300 °C (ethyl acetate-n-
100%). Mp 201-204 °C (ethyl acetate-n-hexane). [R]27
D
-22.9 (c 0.610 CHCl3). MS (FAB, NBA) m/z 811 (M+ + 1).
UV-vis (CHCl3) λmax (ꢀ) 290 nm (3.2 × 104), 303 nm (3.6 ×
104). IR (KBr) 2932, 2864, 1642 cm-1
.
1H NMR (600 MHz,
CDCl3) δ 1.50-1.65 (6 H, m), 1.59 (12 H, br s), 1.66 (6 H, s),
2.17-2.33 (4 H, m), 4.90-5.40 (4 H, br s), 6.27 (2 H, s), 6.75
(2 H, br s), 6.90 (2 H, br s), 7.28 (2 H, d, J ) 7.1 Hz), 7.28-
7.34 (8 H, m), 7.49 (2 H, dd, J ) 7.0, 8.2 Hz), 7.49-7.52 (4 H,
m), 8.14 (2 H, d, J ) 8.2 Hz). 13C NMR (150 MHz, CDCl3) δ
18.6, 18.8, 22.8, 23.2, 26.3, 29.7, 33.3, 44.8, 52.5, 123.3, 123.5,
125.4, 125.8, 126.2, 126.2, 127.7, 127.7, 128.1, 128.4, 130.1,
130.1, 130.8, 131.0, 135.5, 135.8, 136.5, 137.4, 137.5, 148.9,
168.5.
hexane). [R]27 -16.4 (c 0.675 CHCl3). MS (EI, 70 eV) m/z
D
658 (M+, 100%), 643 (M+ - Me, 2). UV-vis (CHCl3) λmax (ꢀ)
290 nm (2.2 × 104), 303 nm (2.6 × 104). IR (KBr) 2926, 2860,
1642 cm-1 1H NMR (600 MHz, CDCl3) δ 1.53-1.60 (6 H, m),
.
(P ,P )-N,N′,N′′,N′′′-Tet r a b en zyl[2+2]cycloa m id e. Mp
>300 °C (ethyl acetate-n-hexane). [R]27 +71.0 (c 0.420
1.74 (6 H, s), 1.95 (6 H, s), 2.00 (6 H, s), 2.20-2.35 (4 H, m),
3.52 (6 H, s), 6.32 (2 H, s), 6.83 (2 H, s), 6.96 (2 H, s), 7.35 (2
H, d, J ) 7.0 Hz), 7.57 (2 H, dd, J ) 7.1, 8.3 Hz), 8.30 (2 H, d,
J ) 8.2 Hz). 13C NMR (150 MHz, CDCl3) δ 18.4, 18.7, 22.8,
23.3, 26.3, 29.7, 33.4, 36.2, 44.8, 123.7, 123.8, 125.3, 126.0,
126.3, 127.7, 128.2, 130.0, 130.9, 131.0, 135.1, 135.3, 136.6,
138.6, 148.8, 168.8.
D
CHCl3). MS (FAB, NBA) m/z 1622 (M+ + 2). UV-vis (CHCl3)
λmax (ꢀ) 309 nm (8.5 × 104). IR (KBr) 2934, 1638 cm-1
.
1H
NMR (600 MHz, CDCl3, 40 °C) δ -1.86 to -1.70 (2 H, m),
-0.47 to -0.36 (2 H, m), 0.02-0.08 (2 H, m), 0.44-0.57 (4 H,
m), 0.90-0.99 (2 H, m), 1.00-1.11 (4 H, m), 1.40 (6 H, s), 1.38-
1.47 (2 H, m), 1.60-1.75 (2 H, m), 1.66 (6 H, s), 1.72 (6 H, s),
1.81 (6 H, s), 1.92 (6 H, s), 2.54 (6 H, s), 4.28 (2 H, d, J ) 13.5
Hz), 4.93 (2 H, d, J ) 13.5 Hz), 5.44 (2 H, d, J ) 13.5 Hz), 5.52
(2 H, d, J ) 13.5 Hz), 6.02 (2 H, s), 6.03 (2 H, s), 6.51 (2 H, s),
6.74 (2 H, s), 7.12 (4 H, d, J ) 7.1 Hz), 7.28 (4 H, t, J ) 7.3
Hz), 7.32 (2 H, t, J ) 7.3 Hz), 7.35 (4 H, d, J ) 7.3 Hz), 7.43
(4 H, t, J ) 7.7 Hz), 7.44 (2 H, d, J ) 6.2 Hz), 7.50 (2 H, s),
7.48-7.55 (5 H, m), 7.63 (2 H, dd, J ) 6.2, 8.2 Hz), 7.73 (2 H,
s), 7.75 (2 H, t, J ) 7.9 Hz), 8.22 (2 H, d, J ) 8.2 Hz), 8.29 (2
H, d, J ) 8.2 Hz). 13C NMR (150 MHz, CDCl3) δ 18.5, 18.6,
19.0, 19.1, 19.6, 22.1, 22.5, 23.0, 24.7, 35.4, 38.8, 46.0, 51.0,
52.7, 122.7, 122.9, 123.6, 123.7, 125.5, 125.8, 125.9, 126.4,
127.0, 127.5, 127.6, 127.8, 128.0, 128.2, 128.3, 128.4, 128.5,
129.5, 129.8, 129.8, 130.3, 130.9, 131.9, 132.8, 133.6, 135.4,
135.6, 135.8, 136.0, 136.1, 136.3, 136.4, 136.7, 137.8, 142.3,
144.0, 149.8, 169.4, 169.4.
(P ,P )-N,N′,N′′,N′′′-Tet r a m et h yl[2+2]cycloa m id e. Mp
>300 °C (ethyl acetate-hexane). [R]27D +80.7 (c 0.205 CHCl3).
MS (FAB, NBA) m/e 1316 (M+ + 2). UV-vis (CHCl3) λmax (ꢀ)
308 nm (5.0 × 104). IR (KBr) 2936,1647 cm-1. The conformers
were separated by silica gel column chromatography (n-
hexane-ethyl acetate) below -10 °C and one major conformer
was isolated. 1H NMR (600 MHz, CDCl3, -30 °C) δ -2.05 to
-1.95 (2 H, m), -0.60 to -0.50 (2 H, m), -0.20 to -0.10 (2 H,
m), 0.25-0.45 (4 H, m), 0.85-1.00 (4 H, m), 1.30-1.40 (2 H,
m), 1.45-1.55 (2 H, m), 1.63 (6 H, s), 1.60-1.70 (2 H, m), 1.75
(6 H, s), 1.97 (6 H, brs), 2.03 (6 H, s), 2.17 (6 H, s), 2.45 (6 H,
s), 3.23 (6 H, s), 3.60 (6 H, brs), 6.12 (2 H, brs), 6.16 (2 H, brs),
6.52 (2 H, s), 6.83 (2 H, s), 7.29 (2 H, s), 7.31 (2 H, d, J ) 7.5
Hz), 7.32 (2 H, s), 7.33 (2 H, d, J ) 7.5 Hz), 7.54 (2 H, dd, J )
7.5, 8.3 Hz), 7.58 (2 H, dd, J ) 7.5, 8.0 Hz), 8.22 (brd, J ) 8.0
Hz), 8.32 (2 H, d, J ) 8.3 Hz). 13C NMR (150 MHz, CDCl3,
-30 °C) δ 17.9, 18.6, 18.7, 19.6, 22.7 (two carbons), 23.1, 24.0,
25.0, 36.0 (two carbons), 37.3, 39.7, 46.0, 122.4, 122.6, 123.5,
124.4, 126.1 (two carbons), 126.3, 126.6, 127.2, 127.5, 128.2,
128.5, 128.5, 128.6 (two carbons), 129.9, 130.1, 131.2, 131.3,
131.9, 133.6, 134.8, 134.9, 135.4, 136.0, 137.1, 138.4, 140.4,
170.8, 170.9. Two aniline carbons at N-C were not detected.
(P ,P )-[2+2]Cycloa m id e Ca ta lyzed Ad d ition of Dieth -
ylzin c to Ar om a tic Ald eh yd e (Gen er a l P r oced u r es).
Under an argon atmosphere, to a mixture of (P,P)-9 (12 mg,
0.01 mmol) and tetrahydrofuran (3 mL) was added 1.6 M
n-butyllithium (0.048 mmol) in hexane (0.03 mL) at 0 °C. The
mixture was stirred for 30 min, and an aldehyde (0.20 mmol)
was added. After the mixture was warmed to room temper-
ature, 1 M diethylzinc (0.60 mmol) in hexane (0.6 mL) was
added. The mixture was vigorously stirred for 1 day at room
temperature, when 2 M hydrochloric acid was added. Organic
materials were extracted with chloroform, and the organic
layer was successively washed with water and brine. After
the solution was dried over MgSO4, the solvents were evapo-
rated in vacuo, and the crude product was purified by silica
gel chromatography (n-hexane-ethyl acetate), giving an opti-
cally active secondary alcohol. The (P,P)-9 was recovered
(>70%). Spectral data of the secondary alcohols were in
accordance with the reported data. The optical purity was
determined by HPLC analysis using Daicel Chiralcel OB-H
(10% 2-propanol in n-hexane). The absolute configuration was
determined according to the literature.
(P ,P ,P )-N ,N ′,N ′′,N ′′′,N ′′′′,N ′′′′′-H e x a m e t h y l[3+3]-
cycloa m id e. Mp >300 °C (ethyl acetate-n-hexane). [R]27
D
+74.9 (c 1.58, CHCl3). Calcd for C138H138O6N6‚8H2O: C, 78.16;
H, 7.32; N, 3.96%. Found: C, 78.32; H, 7.22; N, 3.86%.
Found: C, 77.37; H, 6.97; N, 3.72%. Found: C, 77.79; H, 6.97;
N, 3.95%. Found: C, 78.11; H, 7.26; N, 4.18%. The analytical
sample was prepared by precipitating from ethyl acetate by
adding hexane and dried at 80 °C/1 mmHg for 1 day. MS
(FAB, NBA) m/z 1977 (M+ + 3). UV-vis (CHCl3) λmax (ꢀ) 303
nm (7.8 × 104). IR (KBr) 2928, 1651 cm-1
.
(P ,P ,P ,P )-N,N′,N′′,N′′′,N′′′′,N′′′′′,N′′′′′′,N′′′′′′′-Octa m eth yl-
[4+4]cycloa m id e. Mp >300 °C (ethyl acetate-n-hexane).
[R]27D +69 (c 0.21, CHCl3). Calcd for C184H184O8N8‚13H2O: C,
77.01; H, 7.38; N, 3.90%. Found: C, 76.49; H, 7.12; N, 3.69%.
Found: C, 76.91; H, 7.17; N, 3.64%. Found: C, 77.44; H, 7.19;
N, 4.04%. The analytical sample was prepared by precipitat-
ing from ethyl acetate by adding hexane and dried at 80 °C/1
(R)-1-P h en yl-1-p r op a n ol. [R]25 +16 (c 0.97, CHCl3).
D
Literature19 [R]D -45.45 (c 5.2, CHCl3), (S)-configuration.
(R)-1-(p-Meth oxyp h en yl)-1-eth a n ol. [R]22 +11 (c 1.9,
D