A facile synthesis of 3 or 3,3′-substituted binaphthols and their applications in the asymmetric addition of diethylzinc to aldehydes

Article abstract of DOI:10.1016/j.jorganchem.2005.12.042

By using a direct ortho-lithiation, the ligands (S)-3-methoxymethyl-1, 1′-bi-2-naphthol [(S)-1], (S)-3,3′-bis(methoxymethyl)-1,1′-bi- 2-naphthol [(S)-2], (S)-3-(quinolin-2-yl)-1,1′-bi-2-naphthol [(S)-3] and (S)-3,3′-bis(quinolin-2-yl)-1,1′-bi-2-naphthol [(S)-4] have been synthesized. (S)-1 and (S)-3 show moderate catalytic properties for the asymmetric diethylzinc addition to aromatic aldehydes.

Full text of DOI:10.1016/j.jorganchem.2005.12.042

Journal of Organometallic Chemistry 691 (2006) 1282–1287
www.elsevier.com/locate/jorganchem
A facile synthesis of 3 or 3,30-substituted binaphthols and
their applications in the asymmetric addition of diethylzinc to aldehydes
*
Qun-Sheng Guo, Yong-Na Lu, Bing Liu, Jian Xiao, Jin-Shan Li
State Key Laboratory of Elenmento-Organic Chemistry, Nankai University, Tianjin 300071, PR China
Received 27 September 2005; accepted 1 December 2005
Available online 24 January 2006
Abstract
By using a direct ortho-lithiation, the ligands (S)-3-methoxymethyl-1,10-bi-2-naphthol [(S)-1], (S)-3,30-bis(methoxymethyl)-1,10-bi-2-
naphthol [(S)-2], (S)-3-(quinolin-2-yl)-1,10-bi-2-naphthol [(S)-3] and (S)-3,30-bis(quinolin-2-yl)-1,10-bi-2-naphthol [(S)-4] have been syn-
thesized. (S)-1 and (S)-3 show moderate catalytic properties for the asymmetric diethylzinc addition to aromatic aldehydes.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Lithiation; BINOL; Quinoline; Asymmetric catalysis
1. Introduction
cross-coupling reaction. Heteroaromatic bromides, such
as 2-bromopyridine and 2-bromothiophene, were also tried
for the preparation of 3,30-bis(heteroaryl)-BINOLs; how-
ever, only low yields were obtained. Ohta and co-workers
preparied 3,30-bis(2-oxazolyl)-1,10-bi-2-naphthol (BINOL-
Box) [6]. Gao and co-workers synthesized bis-binaphthyl
units containing 2,20-bipyridines via Suzuki cross-coupling
reaction [7].
In this paper, we report the synthesis of four modified
BINOL ligands (S)-1, (S)-2, (S)-3 and (S)-4 by directed
ortho-lithiation (Fig. 1). (S)-1 and (S)-2 are known com-
pounds [8] synthesized by the reaction of 3-hydroxy-
methyl-BINOL or 3,30-bis (hydroxymethyl)-BINOL with
iodomethane in the presence of base. But the new facile
synthetic approach is first reported by us.
Application of 1,10-bi-2-naphthol (BINOL) and its
derivatives in asymmetric catalysis has been extensively
studied [1]. Substituents at the 3-position of BINOL are
normally introduced via a two-step protocol that involves
treatment of a suitably protected BINOL with an organoli-
thium reagent, followed by reaction with an electrophile.
Cram and co-workers synthesized two optical pure 3,30-
diaryl-substituted BINOLs by a Grignard cross-coupling
reaction of 3,30-dibromo-BINOL dimethyl ether and aryl-
magnesium bromides [2]. Snieckus and co-workers
reported an expedient synthetic route to 3 or 3,30-substi-
tuted-1,10-bi-2-naphthols by directed ortho-metalation
and Suzuki cross-coupling methods [3]. Qian’s group
synthesized (S)-3,30-bis(methoxyethyl)-BINOL from (S)-
BINOL in four steps [4].
2. Results and discussion
Substituted BINOL ligands by introducing heteroaro-
matic groups at the 3 or 3,30-positions were less reported.
Jørgensen et al. [5] reported the synthesis of 3,30-diaryl-
BINOLs by the reaction of 3,30-diboronic acid of bis-
(methoxy)-BINOL with aromatic bromides by a Suzuki
The synthetic route to ligands (S)-1, (S)-2, (S)-3 and
(S)-4 is outlined in Scheme 1. The hydroxyl groups of
(S)-BINOL were protected with methoxymethyl (MOM)
groups to afford (S)-2,20-bis(methoxymethoxy)-1,10-
binaphthalene (S)-5 [9].
*
The lithium salt of (S)-5 reacted with chloromethyl
methyl ether to afford (S)-3-(methoxymethyl)-2,20-
Corresponding author. Fax: +86 22 2350 3438.
E-mail address: jinshan_li2001@yahoo.com.cn (J.-S. Li).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.12.042

Q.-S. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 1282–1287
1283
N
CH OCH
2
3
CH OCH
2
3
OH
OH
N
OH
OH
OH
OH
OH
OH
N
CH OCH
2
3
(S)-1
(S)-2
(S)-3
(S)-4
Fig. 1. The 3 or 3,30-substituted binaphthols.
(S)-3,30-bis(quinolin-2-yl)-2,20-bis(methoxymethoxy)-
CH2OCH3
or
1,10-binaphthalene (S)-9. Suzuki cross-coupling reaction
was the general synthetic procedure to introduce aromatic
or heteroaromatic groups at the 3 or 3,30-positions of
BINOL. In this paper, the direct coupling reaction was used
to prepare (S)-8 and (S)-9. After deprotection of (S)-8 and
(S)-9, ligands (S)-3 and (S)-4 were obtained. A pale yellow
crystals of (S)-3 was obtained from THF-ethanol solution.
The crystal structure of (S)-3 was determined by X-ray dif-
fraction as shown in Fig. 2 [11]. The dihedral angle of
C(11)–C(10)–C(9)–N(1) is 2.1ꢁ. The dihedral angle between
the two naphthalene systems is 86.2ꢁ.
a
57%
e
e
OMOM
OMOM
(S)-1
(S)-2
(S)-6
(S)-7
CH2OCH3
OMOM
OMOM
b
80%
CH2OCH3
OMOM
OMOM
The effectiveness of the four ligands in the titanium
complex-catalyzed enantioselective addition of diethylzinc
to 1-naphthaldehyde was tested [12]. The active catalyst
was formed in situ by mixing the ligand with titanium tet-
raisopropoxide in toluene [13]. In this reaction, the molar
ratio of ligand/Ti(OiPr)4/Et2Zn/1-naphthaldehyde was set
up to be 0.2:1.4:3:1. (S)-1 and (S)-3 showed moderate cat-
alytic properties in this reaction. Reducing the amount of
(S)-1 or (S)-3 catalyst from 20% to 5% led to a large
N
(S)-5
e
OMOM
OMOM
c
55%
(S)-3
(S)-8
N
OMOM
OMOM
e
d
86%
(S)-4
N
(S)-9
Scheme 1. Reagents and conditions: a: (i) 1.2 eq n-BuLi, ꢀ78 ꢁC, (ii) 3.3
eq chloromethyl methyl ether, 0 ꢁC ꢁrt; b: (i) 1.9 eq n-BuLi, 0 ꢁC, (ii) 3.4
eq chloromethyl methyl ether, 0 ꢁC ꢁrt; c: (i) 1.2 eq n-BuLi, ꢀ78 ꢁC, (ii)
1.8 eq quinoline, 0 ꢁC, (iii) PhNO2, H2O, reflux; d: (i) 3.0 eq n-BuLi,
ꢀ78 ꢁC, (ii) 4.0 eq quinoline, 0 ꢁC, (iii) PhNO2, H2O, reflux; e: CH2Cl2,
CH3OH, 6 N HCl, rt.
bis(methoxymethoxy)-1,10-binaphthalene (S)-6 or (S)-3,30-
bis(methoxymethyl)-2,20-bis(methoxymethoxy)-1,10-binaph-
thalene (S)-7. Such a direct C–C coupling reaction of
chloromethyl methyl ether with aryl lithium has never been
reported. After deprotection of (S)-6 and (S)-7, ligands
(S)-1 and (S)-2 were obtained.
The lithium salt of (S)-5 reacted with quinoline, followed
by hydrolysis and oxidation [10] to produce (S)-3-(quinolin-
2-yl)-2,20-bis(methoxymethoxy)-1,10-binaphthalene (S)-8
Fig. 2. The molecular structure of (S)-3 including one THF molecule.

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Q.-S. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 1282–1287
Table 1
Catalytic asymmetric addition of diethylzinc (1.0 M in toluene) to 1-naphthaldehyde
HO
∗
CHO
i
*
Ti(O Pr) /L
4
+
Et Zn
2
toluene
a
*
Entry
L
Yield (%)b
[a]D (c, solvent)
ee (%)c
1
2
3
4
5
6
7
8
a
(S)-1
(S)-2
(S)-3
(S)-4
(S)-1d
(S)-1e
(S)-3d
(S)-3e
94
99
78
91
83
85
79
87
ꢀ48.0 (1.76, CHCl3)
ꢀ28.7 (1.48, CHCl3)
ꢀ43.2 (1.08, CHCl3)
ꢀ14.52 (1.24, CHCl3)
ꢀ43.6 (0.93, CHCl3)
ꢀ41.6 (0.68, CHCl3)
ꢀ37.1 (0.76, CHCl3)
ꢀ31.0 (0.48, CHCl3)
76 (80)
45 (51)
68 (71)
23
71
66
59
49
L /Ti(OiPr)4/Et2Zn/1-naphthaldehyde = 0.2:1.4:3:1; Reaction temperature: 0 ꢁC; Reaction time: 5 h.
*
b
c
Isolated yield.
Based on the reported value of [a]D +45.5 (c = 0.8, CHCl3) in 74% e.e. for (R)-1-(10-naphthyl)-1-propanol [14]. Data in brackets were determined by
GC analysis using a chiral column (Chrompack Chirasil-DEX-CB column) [15].
d
10 mol% of catalyst was used.
5 mol% of catalyst was used.
e
Table 2
Enantioselective addition of diethylzinc to aldehydes with (S)-1 and (S)-3a
O
OH
i
Ti(O Pr) /L*
4
+
Et Zn
∗
2
R
H
toluene
R
Entry
L
*
R
Yield (%)b
[a]D (c, solvent)
ee (%)c
1
2
3
4
5
6
7
8
9
10
11
12
a
(S)-1
(S)-1
(S)-1
(S)-1
(S)-1
(S)-1
(S)-3
(S)-3
(S)-3
(S)-3
(S)-3
(S)-3
Ph
p-ClC6H4
p-BrC6H4
99
95
89
99
95
94
68
83
76
82
84
78
ꢀ35.9 (0.96, CHCl3)
ꢀ16.5 (1.33, PhH)
ꢀ14.24 (1.72, PhH)
ꢀ18.9 (1.0, PhH)
74
66
81
55 (59)
75
76 (80)
69
69
79
64 (69)
83
p-MeOC6H4
o-MeOC6H4
1-naphthyl
Ph
p-ClC6H4
p-BrC6H4
p-MeOC6H4
o-MeOC6H4
1-naphthyl
ꢀ40.6 (1.20, Ph-CH3)
ꢀ48.0 (1.76, CHCl3)
ꢀ33.3 (0.53, CHCl3)
ꢀ17.5 (1.04, PhH)
ꢀ13.9 (1.07, PhH)
ꢀ22.1 (0.14, PhH)
ꢀ44.9 (1.15, Ph-CH3)
ꢀ43.2 (1.08, CHCl3)
68
L /Ti(OiPr)4/Et2Zn/aldehyde = 0.2:1.4:3:1; Solvent: toluene; Reaction temperature: 0 ꢁC; Reaction time: 5 h.
*
b
c
Isolated yield.
Based on the reported value of [a]D ꢀ47.6 (c = 6.11, CHCl3) in 98% ee for (S)-1-phenyl-1-propanol [16]; [a]D ꢀ28.2 (c = 5.01, PhH) in 100% e.e. for (S)-
1-(40-chlorophenyl)-1-propanol [17]; [a]D +13.33 (c = 1.0, PhH) in 76% e.e. for (R)-1-(40-bromophenyl)-1-propanol [18]; [a]D ꢀ34.6 (c = 5.0, PhH) in 90%
ee for (S)-1-(40- methoxyphenyl)-1-propanol [19]; [a]D ꢀ44.9 (c = 1, toluene) in 83% e.e. for (S)-1-(20-methoxyphenyl)-1-propanol [20]; [a]D +45.5 (c = 0.8,
CHCl3) in 74% e.e. for (R)-1-(10-naphthyl)-1-propanol [14]. Data in brackets were determined by GC analysis using a chiral column (Chrompack Chirasil-
DEX-CB column) [15].
decrease in the enantioselectivity. The results were col-
lected in Table 1.
of diethylzinc to aldehydes to give alcohols in high yields
and good e.e. values.
With the ligands (S)-1 and (S)-3, we also examined a
number of aromatic aldehydes for the enantioselective
ethylation with Et2Zn (Table 2).
4. Experimental section
4.1. General
3. Conclusions
1
The H and 13C NMR spectra were recorded on a Bru-
We have synthesized four modified-BINOL ligands (S)-
1, (S)-2, (S)-3 and (S)-4 from (S)-BINOL through a very
convenient route and used them in asymmetric addition
ker AC-300 instrument in CDCl3 solution with TMS as
internal standard. Optical rotations were measured on a
Perkin–Elmer 241 polarimeter. IR spectra were recorded

Q.-S. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 1282–1287
1285
as KBr plates on a Bruker Equinox 55 spectrometer. Ele-
mental analysis was performed with a Yanaco CHN Cor-
der MT-3 elemental analyzer. All experiments which are
sensitive to moisture or air were carried out under an argon
atmosphere using standard Schlenk techniques. All anhy-
drous solvents were purified and dried by standard tech-
niques just before use.
with petroleum ether/ethyl acetate (5/1) as eluent to give
25
(S)-7 (0.99 g, 80% yield) as a colorless oil. ½aꢂD ¼ ꢀ125:1
1
(c = 0.53, CH2Cl2). H NMR (300 MHz, CDCl3): d 2.82
(s, 6H), 3.54 (s, 6H), 4.49 (d, J = 5.7 Hz, 2H), 4.61 (d,
J = 6.0 Hz, 2H), 4.81 (s, 4H), 7.21–7.39 (m, 6H), 7.88 (d,
J = 8.1 Hz, 2H), 8.07 (s, 2H) ppm. 13C NMR (75 MHz,
CDCl3): d 58.66, 70.52, 99.39, 125.16, 125.35, 126.11,
126.45, 128.03, 128.69, 130.81, 131.87, 133.73, 152.10
ppm. IR (KBr): m = 3056, 1446, 1360, 1162, 1100,
752 cmꢀ1. Anal. Calc. for C28H30O6 (462.53): C, 72.71;
H, 6.54. Found: C, 73.00; H, 6.61%.
4.2. Synthesis of (S)-3-(methoxymethyl)-2,20-
bis(methoxymethoxy)-1,10-binaphthalene [(S)-6]
To a solution of 5 (2.244 g, 6 mmol) in anhydrous THF
(60 mL) was added n-BuLi (4.6 mL, 7.2 mmol, 1.57 M
solution in hexane) at ꢀ78 ꢁC under argon and the reaction
mixture was allowed to warm to room temperature and
stirred for 2 h. The resulting solution was cooled to 0 ꢁC
and chloromethyl methyl ether (1.5 mL, 20 mmol) in
THF (10 mL) was added dropwise in 5 min. The mixture
was then warmed to room temperature and stirred for
another 5 h. Aqueous NaHCO3 (40 ml) was added to the
mixture to quench the reaction. The organic layer was sep-
arated and the aqueous layer was extracted with EtOAc.
The combined organic phases were dried over MgSO4.
After removal of the solvent, the residue was submitted
to column chromatographic separation on silica gel with
petroleum ether/ethyl acetate (7/1) as eluent to give (S)-6
4.4. Synthesis of (S)-3-(quinolin-2-yl)-2,20-
bis(methoxymethoxy)-1,10-binaphthalene [(S)-8]
To a solution of 5 (2.244 g, 6 mmol) in anhydrous THF
(50 mL) was added n-BuLi (5.2 mL, 7.28 mmol, 1.4 M
solution in hexane) at ꢀ78 ꢁC under argon and the reac-
tion mixture was allowed to warm to room temperature
and stirred for 4 h. The resulting solution was cooled to
0 ꢁC and quinoline (1.3 mL, 11 mmol) in THF (5 mL)
was added dropwise in 5 min. The mixture was then
warmed to room temperature and stirred for another
12 h. Nitrobenzene (3 mL) and water (5 mL) were added
and the mixture was refluxed for 20 min. After cooling
to room temperature, water (30 mL) was added to the
mixture. The organic layer was separated and the aqueous
layer was extracted with EtOAc. The combined organic
phases were dried over MgSO4. After removal of the sol-
vent, the residue was submitted to column chromato-
graphic separation on silica gel with petroleum ether/
ethyl acetate (5/1) as eluent to give (S)-8 (1.64 g, 55%
25
(1.43 g, 57% yield) as a colorless oil. ½aꢂD ¼ ꢀ86:9
1
(c = 1.14, CH2Cl2). H NMR (300 MHz, CDCl3): d 2.88
(s, 3H), 3.14 (s, 3H), 3.56 (s, 3H), 4.57 (d, J = 5.7 Hz,
1H), 4.65 (d, J = 6.34 Hz, 1H), 4.81 (s, 2H), 5.01 (d,
J = 6.6 Hz, 1H), 5.12 (d, J = 6.9 Hz, 1H), 7.16–7.41 (m,
6H), 7.58 (d, J = 9.0 Hz, 1H), 7.85–7.98 (m, 1H), 8.04 (s,
1H) ppm. 13C NMR (75 MHz, CDCl3): d 56.21, 56.87,
58.91, 70.86, 95.12, 99.59, 116.78, 121.00, 124.43, 125.28,
125.65, 125.81, 125.95, 126.32, 127.01, 128.14, 128.23,
128.59, 129.90, 130.11, 131.15, 132.00, 133.74, 134.28,
152.07, 153.11 ppm. IR (KBr): m = 3056, 1625, 1598,
1156, 1091, 796, 746 cmꢀ1. Anal. Calc. for C26H26O5
(418.48): C, 74.62; H, 6.26. Found: C, 74.23; H, 6.43%.
25
yield) as a pale yellow oil. ½aꢂD ¼ ꢀ22:8 (c = 0.82,
CH2Cl2). 1H NMR (300 MHz, CDCl3): d 2.31 (s, 3H),
3.22 (s, 3H), 4.41 (s, 2H), 5.07 (d, J = 6.9 Hz, 1H), 5.17
(d, J = 6.9 Hz, 1H), 7.23–8.05 (m, 15H), 8.20 (d,
J = 8.4 Hz, 1H), 8.26 (d, J = 8.4 Hz, 1H), 8.46 (s, 1H)
ppm. 13C NMR (75 MHz, CDCl3): d 56.04, 56.17, 95.09,
99.33, 116.66, 120.96, 123.60, 124.21, 125.34, 125.80,
125.90, 126.55, 126.64, 126.70, 126.87, 127.16, 127.59,
127.90, 128.81, 129.57, 129.76, 129.83, 131.22, 131.64,
134.21, 134.36, 134.74, 135.57, 148.51, 150.84, 153.06,
157.66 ppm. IR (KBr): m = 3053, 2949, 2889, 2828, 1596,
4.3. Synthesis of (S)-3,30-bis(methoxymethyl)-2,20-
bis(methoxymethoxy)-1,10-binaphthalene [(S)-7]
To a solution of 5 (1.0 g, 2.67 mmol) in anhydrous THF
(50 mL) was added n-BuLi (3.6 mL, 5.0 mmol, 1.4 M solu-
tion in hexane) at ꢀ78 ꢁC under argon and the reaction
mixture was allowed to warm to room temperature and
stirred for 4 h. The resulting solution was cooled to 0 ꢁC
and chloromethyl methyl ether (0.7 mL, 9.2 mmol) in
THF (5 mL) was added dropwise in 5 min. The mixture
was then warmed to room temperature and stirred for
another 5 h. Aqueous NaHCO3 (30 mL) was added to
the mixture to quench the reaction. The organic layer
was separated and the aqueous layer was extracted with
EtOAc. The combined organic phases were dried over
MgSO4. After removal of the solvent, the residue was sub-
mitted to column chromatographic separation on silica gel
1500, 1522, 1016, 822, 754 cmꢀ1
. Anal. Calc. for
C33H27NO4 (501.57): C, 79.02; H, 5.43; N, 2.79. Found:
C, 78.91; H, 5.61; N, 2.78%.
4.5. Synthesis of (S)-3,30-bis(quinolin-2-yl)-2,20-
bis(methoxymethoxy)-1,10-binaphthalene [(S)-9]
To a solution of 5 (1.87 g, 5 mmol) in anhydrous THF
(60 mL) was added n-BuLi (14 mL, 15 mmol, 1.07 M solu-
tion in hexane) at 0 ꢁC under argon and the reaction mixture
was allowed to warm to room temperature and stirred for
4 h. The resulting solution was cooled to 0 ꢁC and quinoline
(2.58 g, 20 mmol) in THF (10 mL) was added dropwise in
5 min. The mixture was then warmed to room temperature

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Q.-S. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 1282–1287
and stirred for another 12 h. Nitrobenzene (5 mL) and water
(10 mL) were added and the mixture was refluxed for 30 min.
After cooling to room temperature, water (30 mL) was
added to the mixture. The organic layer was separated and
the aqueous layer was extracted with EtOAc. The combined
organic phases were dried over MgSO4. After removal of the
solvent, the residue was submitted to column chromato-
graphic separation on silica gel with petroleum ether/ethyl
acetate (4/1) as eluent to give (S)-9 (2.71 g, 86% yield) as a
4.6.3. (S)-3-(quinolin-2-yl)-1,10-bi-2-naphthol [(S)-3]
25
Yellow powder. M.p. > 300 ꢁC; ½aꢂD ¼ þ72:86 (c =
0.56, CH2Cl2). 1H NMR (300 MHz, CDCl3): d 5.24 (s,
6H), 4.49 (s, 1H), 7.16–7.42 (m, 8H), 7.58 (t, J = 8.4 Hz,
1H), 7.72 (t, J = 8.1 Hz, 1H), 7.86–8.00 (m, 4H), 8.39 (d,
2H), 8.74 (s, 1H), 15.55 (s, 1H) ppm. 13C NMR
(75 MHz, CDCl3): d 114.50, 115.27, 117.74, 117.81,
121.54, 123.26, 123.85, 124.57, 124.94, 126.49, 126.87,
127.29, 127.58, 127.70, 127.75, 128.26, 128.55, 129.07,
129.40, 129.94, 130.85, 133.71. 135.60, 138.13, 144.70,
151.50, 156.40, 157.44 ppm. IR (KBr): m = 3510, 3052,
1600, 1507, 1344, 1204, 819, 746 cmꢀ1. Anal. Calc. for
C29H19NO2 (413.47): C, 84.24; H, 4.63; N, 3.39. Found:
C, 83.57; H, 4.61; N, 3.54%.
25
yellow oil. ½aꢂD ¼ þ72:86 (c = 0.56, CH2Cl2). 1H NMR
(300 MHz, CDCl3): d 2.44 (s, 6H), 4.49 (d, J = 6.3 Hz,
2H), 4.57 (d, J = 5.1 Hz, 2H), 7.31 (s, 2H), 7.32 (s, 2H),
7.42–7.47 (m, 2H), 7.57 (t, J = 7.5 Hz, 2H), 7.77 (t, J =
6.9 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 8.01 (d, J = 8.1 Hz,
2H), 8.12 (d, J = 8.4 Hz, 2H), 8.23 (d, J = 8.4 Hz, 2H),
8.29 (d, J = 8.1 Hz, 2H), 8.50 (s, 2H) ppm. 13C NMR
(75 MHz, CDCl3): d 56.28, 99.39, 123.48, 125.46, 126.34,
126.59, 127.12, 127.20, 127.58, 128.74, 129.61, 129.67,
129.73, 131.04, 132.07, 134.52, 135.71, 148.50, 151.21,
157.47 ppm. IR (KBr): m = 3054, 2945, 1598, 1498, 1154,
834, 756 cmꢀ1. Anal. Calc. for C42H32N2O4 (628.71): C,
80.24; H, 5.13; N, 4.46. Found: C, 80.08; H, 5.36; N, 4.66%.
4.6.4. (S)-3,30-bis(quinolin-2-yl)-1,10-bi-2-naphthol
[(S)-4]
25
Yellow powder. M.p. > 300 ꢁC; ½aꢂD ¼ þ380:24 (c =
1
0.41, CH2Cl2). H NMR (300 MHz, CDCl3): d 7.26–7.35
(m, 6H), 7.55 (t, J = 7.5 Hz, 2H), 7.68 (t, J = 6.9 Hz,
2H), 7.87 (d, J = 7.8 Hz, 2H), 7.98 (m, 4H), 8.40 (s, 4H),
8.74 (s, 2H), 15.23 (s, 2H) ppm. 13C NMR (75 MHz,
CDCl3): d 118.11, 118.45, 121.50, 123.28, 124.71, 126.73,
126.92, 127.53, 127.71, 127.80, 127.94, 128.34, 129.07,
130.50, 135.62, 137.79, 144.81, 155.32, 158.09 ppm. IR
(KBr): m = 3423, 3054, 2969, 1602, 1506, 1146, 832,
749 cmꢀ1. Anal. Calc. for C38H24N2O2 (540.61): C, 84.42;
H, 4.47; N, 5.18. Found: C, 83.53; H, 4.80; N, 5.64%.
4.6. Synthesis of (S)-3-(methoxymethyl)-1,10-bi-2-naphthol
[(S)-1]: Deprotection of the MOM groups; typical
procedure
To a solution of (S)-6 (1.43 g, 3.42 mmol) in CH2Cl2
(5 mL) and MeOH (20 mL) was added 6 N HCl (5 mL)
and the mixture was stirred at room temperature for
12 h. The mixture was poured into water (40 mL),
extracted with CH2Cl2, washed with water and saturated
NaHCO3, dried (Na2SO4), and concentrated in vacuo.
4.7. A typical procedure for the asymmetric addition of
diethylzinc to benzaldehyde
Titanium tetraisopropoxide (0.43 mL, 1.25 mmol) was
added to a solution of (S)-1 (0.059 g, 0.179 mmol) in
3 mL of toluene at room temperature and was stirred for
15 min followed by the addition of diethylzinc (2.7 mL,
1.0 M solution in toluene) with continued stirring for
15 min. The solution was cooled to 0 ꢁC and benzaldehyde
(0.09 mL, 0.90 mmol) was introduced with a syringe. The
reaction mixture was stirred at 0 ꢁC for 5 h. The reaction
was quenched with 20 mL of saturated NH4Cl solution,
the mixture was extracted with ethyl acetate. The combined
organic layers were dried over MgSO4 and concentrated to
solvent free. The residue was purified by column chroma-
tography on silica gel affording 1-phenyl-1-propanol as a
colorless liquid. The optical rotation was measured.
4.6.1. (S)-3-(methoxymethyl)-1,10-bi-2-naphthol [(S)-1]
25
1
Colorless foam. ½aꢂD ¼ ꢀ18:55 (c = 0.55, CH2Cl2). H
NMR (300 MHz, CDCl3): d 3.46 (s, 3H), 4.77 (s, 2H), 5.13
(b, 1H), 6.59 (s, 1H), 7.10–7.28 (m, 7H), 7.82–7.97 (m, 4H)
ppm. 13C NMR (75 MHz, CDCl3): d 58.67, 72.26, 112.40,
112.68, 117.75, 123.72, 124.21, 124.44, 124.54, 125.87,
127.06, 127.29, 128.28, 128.37, 128.99, 129.16, 129.41,
130.76, 133.52, 133.62, 151.95, 152.19 ppm. IR (KBr): m =
3392, 3058, 1621, 1597, 1146, 1111, 817, 750 cmꢀ1. Anal.
Calc. for C22H18O3 (330.38): C, 79.98; H, 5.49. Found: C,
79.36; H, 5.23%.
4.6.2. (S)-3,30-bis(methoxymethyl)-1,10-bi-2-naphthol
[(S)-2]
Acknowledgements
25
White powder. M.p. 140–142 ꢁC; ½aꢂD ¼ ꢀ62:86 (c = 0.49,
1
CH2Cl2). H NMR (300 MHz, CDCl3): d 3.50 (s, 6H), 4.82
This work was supported by the National Natural Sci-
ence Foundation of China (grant No. 20372037).
(d, J = 4.5 Hz, 4H), 6.64 (s, 2H), 7.13 (d, J = 8.1 Hz, 2H),
7.21–7.34 (m, 4H), 7.83 (s, 1H), 7.85 (b, 3H) ppm. 13C
NMR (75 MHz, CDCl3): d 58.58, 72.49, 114.04, 123.87,
124.60, 125.61, 126.89, 128.19, 128.58, 128.85, 133.58,
151.40 ppm. IR (KBr): m = 3283, 3063, 1445, 1388, 1205,
1093, 748 cmꢀ1. Anal. Calc. for C24H22O4 (374.43): C,
76.99; H, 5.92. Found: C, 76.72; H, 6.08%.
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