9040
K. H. Kim et al. / Tetrahedron 60 (2004) 9037–9042
2
5
eluted with ethyl acetate/hexanes to give the enantiomeri-
0
oil; [a] 88.5 (c 0.37, THF); IR (CHCl ) 3459, 3367 (NH ),
D 3 2
K1 1
1619, 1597 (C]C, aromatic) cm ; H NMR (300 MHz,
CDCl ) d 0.80 (td, JZ7.2, 2.1 Hz, 6H), 1.23–1.38 (m, 4H),
cally pure N,N -dialkylated diamines and N-monoalkylated
diamines.
3
1
.47 (m, 1H), 1.58–1.75 (m, 8H), 2.11–2.30 (m, 4H), 2.72
0
4% yield as a white solid (mp 158–159 8C); [a] 137.3 (c
4
7
1
3
.2.1. (R)-N-Isopropyl-1,1-binaphthyl-2,2 -diamine (6d).
(m, 4H), 3.19 (br, 3H), 6.51 (d, JZ8.1 Hz, 1H), 6.63 (d, JZ
2
5
8.4 Hz, 1H), 6.91 (d, JZ8.1 Hz, 1H), 6.99 (d, JZ8.1 Hz,
D
8
.33, THF) {lit. [a] 137 (c 0.2, THF)}; IR (CHCl ) 3473,
13
1H); C NMR (75 MHz, CDCl ) d 10.16, 10.34, 23.56,
D
3
3
K1
380 (NH ), 1620, 1596 (C]C, aromatic) cm ; H NMR
1
23.67 (2C), 23.84, 26.99, 27.01, 27.19, 27.37, 29.51, 29.65,
54.99, 108.31, 113.26, 121.31, 122.05, 127.37, 127.79,
129.30, 129.44, 136.42, 136.79, 142.08, 143.23. Anal. Calcd
2
(
300 MHz, CDCl ) d 1.01 (d, JZ6.3 Hz, 3H), 1.08 (d, JZ
3
6
.3 Hz, 3H), 3.44 (br, 1H), 3.68 (br, 2H), 3.83 (m, 1H), 6.99
(
4
d, JZ7.5 Hz, 1H), 7.07 (d, JZ8.1 Hz, 1H), 7.15–7.24 (m,
H), 7.31 (d, JZ9.0 Hz, 2H), 7.78–7.91 (m, 4H); C NMR
for C25H N : C, 82.82; H, 9.45; N, 7.73. Found: C, 82.961;
34 2
H, 9.61; N, 7.79.
1
3
(
75 MHz, CDCl ) d 23.45, 23.60, 45.02, 112.53, 113.09,
3
1
1
1
15.55, 118.48, 122.17, 122.62, 124.06, 124.35, 126.90,
26.95, 127.89, 128.28, 128.32, 128.68, 129.72, 129.81,
33.96, 134.17, 143.15, 144.28. Anal. Calcd for C H N :
4.3. Procedures for the synthesis of diamine ligands 6c,
7b and 7c.
23 22 2
0 0
4.3.1. (R)-2-Amino-2 -(1-pyrrolinyl)-1,1 -binaphthyl
C, 84.63; H, 6.79; N, 8.58. Found: C, 84.57; H, 6.88; N,
8
1
0a
.60.
(6c). To a solution of (R)-BINAM (6a)
1
(300 mg,
.056 mmol), NaI (16 mg, 0.1056 mmol), and potassium
0
4
.2.2. (R)-N-Cyclohexyl-1,1-binaphthyl-2,2 -diamine
carbonate (365 mg, 2.64 mmol) in DMF (22 ml) was added
1,4-dibromobutane (126 ml, 1.506 mmol) slowly. The reac-
tion mixture was stirred for 36 h at 70 8C. After cooling the
mixture to room temperature, the reaction mixture was
added with brine followed by extraction with dichloro-
methane (30 ml!3). The combined organic layers were
dried (Na SO ) and concentrated in vacuo. The residue was
2
5
(
1
6e). 32% yield as a white solid (mp 223–224 8C); [a]
D
8
21.9 (c 1.0, THF) {lit. [a] 122 (c 0.4, THF)}; IR (CHCl )
D 3
K1 1
475, 3377 (NH ), 1618, 1597 (C]C, aromatic) cm ; H
3
NMR (300 MHz, CDCl ) d 0.76–1.11 (m, 3H), 1.19–1.37
2
3
(
m, 2H), 1.52–1.66 (m, 3H), 1.86–1.98 (m, 2H), 3.41 (m,
1
8
H), 3.65 (br, 3H), 6.98 (d, JZ6.6 Hz, 1H), 7.06 (d, JZ
.1 Hz, 1H), 7.13–7.31 (m, 6H), 7.76–7.88 (m, 4H);
2
4
13
C
purified by flash column chromatography on silica gel
eluted with ethyl acetate/hexanes (1:16) to give 6c (71 mg,
NMR (75 MHz, CDCl ) d 25.19, 25.26, 25.90, 33.85, 34.02,
3
25
5
1
1
2.39, 112.59, 112.90, 115.51, 118.47, 122.07, 122.60,
24.00, 124.39, 126.86, 126.93, 127.84, 128.26, 128.28,
28.67, 129.64, 129.64, 134.01, 134.18, 143.13, 144.00.
20% yield) as a white solid (mp 99–100 8C): [a] 180.0 (c
1.0, THF); IR (CHCl ) 3464, 3374 (NH ), 1618, 1596
D
3
K1
2
1
(C]C, aromatic) cm ; H NMR (300 MHz, CDCl ) d
3
1
.62–1.70 (m, 4H), 2.90 (m, 2H), 3.14 (m, 2H), 3.75 (br,
0
4
6
1
1
.2.3. (R)-N-(3-Pentyl)-1,1-binaphthyl-2,2 -diamine (6f).
2H), 7.03–7.27 (m, 6H), 7.32 (d, JZ9.0 Hz, 2H), 7.75–7.84
2
5
13
(m, 4H); C NMR (75 MHz, CDCl ) d 26.01 (2C), 49.99
1% yield as a yellowish solid (mp 133–134 8C); [a]D
74.8 (c 1.0, THF); IR (CHCl ) 3460, 3376 (NH ), 1617,
594 (C]C, aromatic) cm ; H NMR (300 MHz, CDCl )
d 0.70 (t, JZ7.5 Hz, 3H), 0.88 (t, JZ7.2 Hz, 3H), 1.24–1.60
m, 4H), 3.46 (m, 1H), 3.61 (br, 1H), 3.71 (br, 1H), 7.01 (d,
JZ6.6 Hz, 1H), 7.14–7.31 (m, 7H), 7.81–7.92 (m, 4H); C
NMR (75 MHz, CDCl ) d 10.15, 10.36, 27.37, 27.50, 55.64,
11.93, 112.72, 114.75, 118.51, 121.80, 122.65, 123.90,
24.54, 126.93, 126.96, 127.52, 128.29, 128.35, 128.71,
29.71, 129.77, 134.16, 134.29, 143.30, 144.59. Anal. Calcd
3
(2C), 112.70, 117.50, 117.99, 118.07, 122.00, 122.26,
124.29, 125.59, 126.61, 126.78, 127.84, 128.03, 128.09,
128.11, 129.01, 129.27, 134.65, 135.42, 142.96, 146.46.
Anal. Calcd for C H N : C, 85.17; H, 6.55; N, 8.28.
3
1
2
K1
3
(
2
4 22 2
1
3
Found: C, 85.18; H, 6.54; N, 8.18.
3
0
binaphthyl-2,2 -diamine (7b). To a solution of the diamine
0
0
0
0
1
1
1
4.3.2. (R)-N-Benzyl-5,5 ,6,6 ,7,7 ,8,8 -octahydro-1,1 -
0
(300 mg, 1.019 mmol) in 10 ml of dichloromethane
1
0b
7a
for C H N : C, 84.70; H, 7.39; N, 7.90. Found: C, 84.77;
2
was added a solution of acetic anhydride (0.11 ml,
1.12 mmol) in 10 ml of dichloromethane slowly for 2 h.
The reaction mixture was stirred for another 1 h and
quenched with 1 N NaOH (20 ml). The mixture was extract
with dichloromethane (20 ml!3), and the combined
5 26 2
H, 7.36; N, 7.75.
.2.4. (R)-N-Isopropyl-5,5 ,6,6 ,7,7 ,8,8 -octahydro-1,1-
binaphthyl-2,2 -diamine (7d). 79% yield as a pale yellow
0
0
0
0
4
0
2
D
5
oil; [a] 80.7 (c 0.32, THF); IR (CHCl ) 3461, 3369 (NH ),
3
organic layers were dried (MgSO ) and concentrated in
4
2
K1
1
680, 1597 (C]C, aromatic) cm ; H NMR(300 MHz,
1
vacuo. The residue was purified by flash column chroma-
tography on silica gel eluted with ethyl acetate/hexanes
(1:3) to give (R)-N-acetyl-H -BINAM (202.6 mg, 68%).
CDCl ) d 1.07 (d, JZ3.0 Hz, 3H), 1.09 (d, JZ3.1 Hz, 3H),
3
1
.62–1.77 (m, 8H), 2.16–2.30 (m, 4H), 2.74 (m, 4H), 3.28
8
(
br, 3H), 3.62 (m, 1H), 6.61 (d, JZ9.0 Hz, 1H), 6.64 (d, JZ
The (R)-N-acetyl-(H )-BINAM (100 mg, 0.3 mmol) was
8
8
1
2
1
1
.1 Hz, 1H), 6.94 (d, JZ8.1 Hz, 1H), 7.01 (d, JZ8.1 Hz,
dissolved with DMF (3 ml), and K CO (42 mg, 0.3 mmol)
2
3
1
H); C NMR (75 MHz, CDCl ) d 23.38, 23.40, 23.57,
3
3
was added to the reaction mixture. Benzyl bromide (36 ml,
0.3 mmol) was added slowly to the reaction mixture, and the
mixture was stirred overnight. The mixture was added with
1 N NaOH (10 ml) and extracted with ethyl acetate
(20 ml!3). The combined organic layers were dried
3.63, 23.72, 23.82, 27.21, 27.41, 29.56, 29.63, 44.48,
09.78, 113.31, 121.93, 122.09, 126.15, 127.77, 129.40,
29.47, 136.33, 136.61, 142.04, 143.03. Anal. Calcd for
C H N : C, 82.59; H, 9.04; N, 8.37. Found: C, 82.40; H,
3 32 2
2
9
.15; N, 8.17.
(MgSO ) and concentrated in vacuo. The residue was
4
dissolved with MeOH (5 ml) and 4 N HCl (5 ml) and the
reaction mixture was heated to reflux overnight. The
reaction mixture was quenched by 1 N NaOH (20 ml),
0
binaphthyl-2,2 -diamine (7e). 63% yield as a pale yellow
0
0
0
4
.2.5. (R)-N-(3-Pentyl)-5,5 ,6,6 ,7,7 ,8,8 -octahydro-1,1-
0