S. Takizawa et al. / Tetrahedron 63 (2007) 6512–6528
6523
2
7
1
9
H), 3.74 (s, 3H), 3.75 (s, 3H), 4.11 (q, J¼7.0 Hz, 2H), 7.00–
.33 (m, 5H), 7.41 (d, J¼6.5 Hz, 1H), 7.44 (d, J¼6.5 Hz,
H), 7.62 (s, 1H), 7.85 (d, J¼9.2 Hz, 1H), 7.89 (d, J¼
(CDCl ): d 1.36–1.41 (m, 4H), 1.55 (t, J¼6.7 Hz, 2H),
3
1.65–1.71 (m, 2H), 2.71 (t, J¼7.8 Hz, 2H), 3.60 (t,
J¼6.5 Hz, 2H), 3.73 (s, 3H), 3.75 (s, 3H), 7.00–7.33 (m,
5H), 7.41 (d, J¼7.2 Hz, 1H), 7.44 (d, J¼7.2 Hz, 1H), 7.62
(s, 1H), 7.85 (d, J¼9.2 Hz, 1H), 7.88 (d, J¼9.2 Hz, 1H),
1
3
.2 Hz, 1H), 7.95 (d, J¼9.2 Hz, 1H). C NMR (CDCl ):
3
d 14.3, 24.9, 28.8, 30.9, 30.9, 34.3, 35.6, 56.8, 56.9, 60.1,
1
3
1
1
1
14.1, 114.2, 119.4, 119.6, 123.3, 125.0, 125.1, 126.1,
26.1, 127.7, 128.6, 129.0, 129.1, 129.2, 132.3, 133.8,
37.3, 154.2, 154.7, 173.5. FABHRMS. Calcd for
7.96 (d, J¼9.2 Hz, 1H). C NMR (CDCl ): d 25.6, 29.1,
3
31.2, 32.7, 35.7, 56.9, 56.9, 62.9, 114.1, 114.2, 119.4,
119.6, 123.3, 125.0, 125.1, 126.1, 127.7, 127.8, 128.6,
129.0, 129.1, 129.2, 132.3, 133.8, 137.5, 154.2, 154.7.
+
C H O [M ]: 456.2301. Found: 456.2292.
0 32 4
3
+
FABHRMS. Calcd for C H O [M ]: 414.2195. Found:
2
8 30 3
4
.7. General procedure for LiAlH reduction
4
414.2188.
To a solution of the above obtained ester (20 mmol) in THF
150 mL) under an argon atmosphere, LiAlH (20 mmol)
was added, followed by stirring at 0 C. The mixture was
stirred until the reaction reached completion as determined
by monitoring with TLC analysis. The reaction was
quenched with water in an ice bath and extracted with EtOAc
4.8. General procedure for conversion of alcohol to
bromide
(
4
ꢀ
To a mixture of the above obtained alcohol (12 mmol) and
PPh (24 mmol) in THF (150 mL) under an argon atmo-
3
ꢀ
sphere, CBr (24 mmol) was added at 0 C. The mixture
4
(
100 mLꢁ3). The organic layer was washed with 1 N HCl
was stirred until the reaction had reached completion as
determined by monitoring with TLC analysis. The reaction
mixture was diluted with hexane, and PPh O was precipi-
tated and filtered through Celite . The filtrate was con-
centrated under vacuum to give an oil, which was
(
filtrate was concentrated under vacuum to give an oil, which
was subjected to column chromatography on SiO with
2
EtOAc/hexane (1/4). The corresponding alcohol was ob-
tained in quantitative yield as colorless oil.
50 mL) and brine (50 mL), then dried over Na SO . The
2
4
3
Ò
subjected to column chromatography on SiO with EtOAc/
2
hexane (1/10) to afford the corresponding bromide as a
yellow oil.
0
ol (n=4). IR (neat): nmax 3393, 3059, 3007, 2934, 2837,
0
4
.7.1. (R)-4-(2,2 -Dimethoxy-1,1 -binaphth-6-yl)butan-1-
0
0
1
1
6
620, 1594, 1505, 1480, 1460, 1351, 1330, 1263, 1178,
148, 1092, 1067, 1047, 1018, 889, 808, 748, 689,
60 cm . [a]D +14.5 (c 1.19, CHCl ). H NMR (CDCl ):
4.8.1. (S)-6-(4-Bromobutyl)-2,2 -dimethoxy-1,1 -binaph-
thalenyl (13a) (n=4). Yield 70%. IR (neat): nmax 3060,
2998, 2933, 2837, 1623, 1593, 1507, 1481, 1462, 1351,
1328, 1263, 1178, 1147, 1134, 1092, 1067, 1047, 1018,
ꢂ1
25
1
3
3
d 1.37 (s, OH), 1.59–1.79 (m, 4H), 2.73 (t, J¼7.6 Hz, 2H),
ꢂ1
25
1
3
7
1
.64 (t, J¼6.3 Hz, 2H), 3.73 (s, 3H), 3.75 (s, 3H), 6.99–
.32 (m, 5H), 7.41 (d, J¼7.0 Hz, 1H), 7.44 (d, J¼7.0 Hz,
H), 7.62 (s, 1H), 7.85 (d, J¼9.2 Hz, 1H), 7.88 (d,
889, 808, 748, 689 cm . [a]D ꢂ14.5 (c 1.12, CHCl ). H
3
NMR (CDCl ): d 1.76–1.97 (m, 4H), 2.74 (t, J¼7.0 Hz,
3
2H), 3.42 (t, J¼6.5 Hz, 2H), 3.75 (s, 3H), 3.76 (s, 3H),
7.00–7.34 (m, 5H), 7.42 (d, J¼5.4 Hz, 1H), 7.45 (d,
J¼5.4 Hz, 1H), 7.63 (s, 1H), 7.86 (d, J¼9.2 Hz, 1H), 7.90
1
3
J¼9.2 Hz, 1H), 7.95 (d, J¼9.2 Hz, 1H).
C NMR
(
CDCl ): d 27.3, 32.4, 35.5, 56.9, 57.0, 62.8, 114.1, 114.2,
3
1
3
1
1
19.4, 119.5, 123.3, 125.1, 126.1, 126.2, 127.7, 127.7,
28.7, 129.0, 129.2, 132.3, 133.8, 137.1, 154.3, 154.7.
(d, J¼9.2 Hz, 1H), 7.97 (d, J¼9.2 Hz, 1H). C NMR
(CDCl ): d 29.6, 32.3, 33.8, 34.8, 56.9, 56.9, 114.0, 114.3,
3
+
FABMS (m/z): 386 [M ]. Anal. Calcd for C H O $2/
6 26 3
119.5, 123.3, 125.1, 125.2, 126.1, 126.3, 127.6, 127.7,
128.7, 129.0, 129.2, 132.4, 133.8, 136.6, 154.3, 154.7.
FABMS (m/z): 448 [M ]. Anal. Calcd for C H BrO $3/
2
3
H O: C, 78.36; H, 6.91. Found: C, 78.18; H, 6.72.
2
+
2
6
25
2
0
0
4
1
1
1
6
.7.2. (S)-5-(2,2 -Dimethoxy-1,1 -binaphth-6-yl)pentan-
-ol (n=5). IR (neat): nmax 3377, 3058, 2999, 2932, 2837,
622, 1593, 1506, 1481, 1460, 1352, 1331, 1256, 1178,
148, 1134, 1094, 1065, 1047, 1018, 885, 806, 748, 689,
7H O: C, 68.32; H, 5.70; Br, 17.48. Found: C, 68.05; H,
2
5.73; Br, 17.56.
0
0
4.8.2. (S)-6-(5-Bromopentyl)-2,2 -dimethoxy-1,1 -
binaphthalenyl (13b) (n=5). Quantitative yield. IR (neat):
nmax 3058, 2999, 2933, 2837, 1622, 1593, 1508, 1480,
1460, 1352, 1329, 1263, 1178, 1148, 1134, 1092, 1067,
ꢂ1
25
1
60 cm . [a]D ꢂ16.1 (c 1.19, CHCl ). H NMR
3
(
CDCl ): d 1.36–1.47 (m, 2H), 1.54–1.75 (m, 4H), 2.71 (t,
3
J¼7.6 Hz, 2H), 3.61 (t, J¼6.5 Hz, 2H), 3.73 (s, 3H), 3.75
ꢂ1
25
(
(
7
(
s, 3H), 7.00–7.33 (m, 5H), 7.41 (d, J¼7.2 Hz, 1H), 7.44
d, J¼7.2 Hz, 1H), 7.62 (s, 1H), 7.85 (d, J¼9.2 Hz, 1H),
1047, 1018, 889, 804, 748, 689 cm . [a]D ꢂ14.7 (c 1.01,
1
CHCl ). H NMR (CDCl ): d 1.45–1.57 (m, 2H), 1.65–
3
3
1
3
.88 (d, J¼9.2 Hz, 1H), 7.95 (d, J¼9.2 Hz, 1H). C NMR
1.77 (m, 2H), 1.85–1.96 (m, 2H), 2.74 (t, J¼7.3 Hz, 2H),
3.40 (t, J¼6.9 Hz, 2H), 3.75 (s, 3H), 3.77 (s, 3H), 7.00–
7.35 (m, 5H), 7.43 (d, J¼5.9 Hz, 1H), 7.46 (d, J¼5.9 Hz,
CDCl ): d 25.5, 31.1, 32.7, 35.8, 56.9, 57.0, 62.9, 114.1,
3
1
1
1
14.3, 119.4, 119.6, 123.3, 125.1, 125.1, 126.1, 126.2,
27.7, 128.6, 129.0, 129.2, 129.2, 132.3, 133.9, 137.4,
54.3, 154.7. FABMS (m/z): 400 [M ]. Anal. Calcd for
1H), 7.65 (s, 1H), 7.88 (d, J¼9.2 Hz, 1H), 7.92 (d,
+
13
J¼9.2 Hz, 1H), 7.98 (d, J¼9.2 Hz, 1H).
C NMR
(CDCl ): d 27.9, 30.4, 32.7, 33.8, 35.6, 56.8, 56.9, 114.1,
C H O $1/3H O: C, 79.77; H, 7.11. Found: C, 79.74; H,
2
7
28
3
2
3
7
.11.
114.2, 119.4, 119.5, 123.3, 125.1, 126.1, 126.2, 127.6,
127.7, 128.6, 129.0, 129.2, 132.3, 133.8, 137.1, 154.3,
154.7. FABHRMS. Calcd for C H BrO [M ]: 462.1194.
Found: 462.1194.
0
ol (n=6). IR (neat): nmax 3356, 3059, 2999, 2930, 2853,
0
+
4
.7.3. (S)-6-(2,2 -Dimethoxy-1,1 -binaphth-6-yl)hexan-1-
2
7
27
2
1
1
6
622, 1593, 1506, 1481, 1460, 1352, 1330, 1254, 1178,
148, 1134, 1094, 1065, 1047, 1020, 889, 806, 748, 689,
0
0
4.8.3. (S)-6-(6-Bromohexyl)-2,2 -dimethoxy-1,1 -binaph-
thalenyl (13c) (n=6). Yield 90%. IR (neat): nmax 3058,
ꢂ1
25
1
64, 592 cm . [a]D ꢂ14.0 (c 0.56, CHCl ). H NMR
3