Synthesis of novel 1-aryl-substituted 8-methoxynaphthalenes and their tendency for atropisomerization

Article abstract of DOI:10.1016/j.tet.2004.01.025

Novel 1-aryl-substituted 8-methoxynaphthalenes were conveniently prepared by using Suzuki-Miyaura cross-coupling as a key reaction. Chemical transformations of the coupled products gave a variety of biaryls bearing various functional groups. The optical behavior of the separated enantiomers of these derivatives was also investigated by HPLC analysis. The optical resolution and determination of absolute configuration of novel binaphtyl derivative were also described. These new compounds may have some potential as mono- or bidentate ligands for metal-catalyzed chemical transformations including asymmetric induction.

Full text of DOI:10.1016/j.tet.2004.01.025

Tetrahedron 60 (2004) 2225–2234
Synthesis of novel 1-aryl-substituted 8-methoxynaphthalenes
and their tendency for atropisomerization
Seiji Yoshikawa, Jun-ichi Odaira, Yuki Kitamura, Ashutosh V. Bedekar, Takumi Furuta and
*
Kiyoshi Tanaka
School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Received 13 December 2003; revised 11 January 2004; accepted 13 January 2004
Abstract—Novel 1-aryl-substituted 8-methoxynaphthalenes were conveniently prepared by using Suzuki–Miyaura cross-coupling as a key
reaction. Chemical transformations of the coupled products gave a variety of biaryls bearing various functional groups. The optical behavior
of the separated enantiomers of these derivatives was also investigated by HPLC analysis. The optical resolution and determination of
absolute configuration of novel binaphtyl derivative were also described. These new compounds may have some potential as mono- or
bidentate ligands for metal-catalyzed chemical transformations including asymmetric induction.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
1,8-disubstituted naphthalene as a catalyst or chiral inducer.
Recently, we reported the preparation of optically active
8,80-difunctionalized 1,10-binaphthyl derivatives5 and their
optical behavior.6 Moreover, the successful use of these
molecules as chiral inducers for asymmetric protonation5a
and asymmetric carbon–carbon bond formation7 as well as
in the chiral recognition of amino acid derivatives8 has also
been reported. Since a specific and interesting peri-
interaction on the naphthalene ring is expected in 1,8-
disubstituted naphthalene derivatives, to examine their
catalytic activity as ligands and their optical behavior as
possible atropisomers, we focused our attention on the
preparation and characterization of new families of 1-aryl-
substituted 8-methoxynaphthalene and related derivatives.9
A preliminary experiment regarding the optical resolution
of the newly synthesized biaryls as well as optical behavior
are also described.
The combination of transition metals and chiral ligands has
greatly contributed to progress in synthetic transformation
to create interesting chiral molecules in optically active
forms. In this context, axially chiral biaryls have played
important roles in asymmetric synthesis as well as chiral
recognition in the field of host–guest chemistry by creating
a specific asymmetric environment around the recognition
sites of substrates involving chiral catalysts, reagents and
host molecules. A specific feature of these derivatives is that
the rigid binaphthyl skeleton has a rather high energy barrier
to atropisomerization even at an elevated temperature and
the functional groups on the naphthyl ring can chelate a
metal ion to create specific chiral conditions for effective
chiral induction. The most widely used compounds of this
typ0e for use as a chiral li0gand or auxiliary are non-racemic
2,2 -difunctionalized 1,1 -binaphthyls,1 such as BINAP,2
MOP3 and BINOL,4 however, the degree of asymmetric
induction and catalytic activity are not universally high, and
indeed are sometimes unsatisfactory in specific cases. This
is why the further development of novel axially chiral
compounds that show strong asymmetric induction is still
required. To develop new ligands or catalysts consisting of
p-systems, both steric and electronic tuning of the biaryl
structures are nece0ssary. Compared to ordinary 2,20-
difunctionalized 1,1 -binaphthyls, there have been few
reported examples of the preparation and use of chiral
2. Results and discussion
2.1. Molecular design and synthetic strategy
To construct 1,8-disubstituted naphthalene as a general key
structural unit, 1-aryl-substituted naphthalene derivatives
possessing an oxygen substituent at the 1-position were
selected as a basic structure, and an additional substituent
(R1) was introduced at the ortho position relative to the
biaryl axis on the aryl ring to prevent free rotation around
the biaryl axis (Fig. 1). In addition to benzene and
naphthalene rings, a pyridine (Y¼N) ring was also a
candidate for the 1-aryl group. As for the substituents R1 and
R2, a wide variety of functional groups, functionalized and
Keywords: Atropisomer; 1,8-Disubstituted naphthalene; Biaryl; Suzuki–
Miyaura coupling.
*
Corresponding author. Tel.: þ81-54-264-5746; fax: þ81-54-264-5745;
e-mail address: tanakaki@u-shizuoka-ken.ac.jp
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.01.025

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S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
Figure 1. Preparation of axially chiral biaryls substituted at peri-positions.
unfunctionalized alkyl groups, including hydroxyl, halogen,
amine, phosphine, ester, ether, aryl, hydroxymethyl, and
methyl groups, were chosen. Due to the steric or electronic
repulsive interaction between these substituents R1 and R2,
the designed molecules were expected to have axial
chirality at least at low temperature. Additionally, in
molecules in which both the R1 and R2 moieties bear
heteroatom substituents, these molecules may function as
effective bidentate ligands through intramolecular chelation
to form a medium-sized ring through chelation with a metal.
Moreover, since both the substituents R1 and R2 face toward
the p systems of the naphthyl and aryl rings, respectively,
the chelated metal may be placed inside the asymmetric
cavity created by the chiral biaryl system, and hence act as
the center of effective catalysts. These molecular conditions
might lead to the creation of novel circumstances in which
high levels of both catalytic activity and asymmetric
induction are realized. Along these lines, synthetic studies
of non-racemic and non-symmetricall0y substituted 1,100-
binaphthalene derivatives including 2,8 -disubstituted 1,1 -
binaphthyls, as well as their excellent activity as chiral
generalized in Figure 1. Compared to the prospect of
introducing a variety of functional groups at the 20 position
of binaphthyl systems, the present synthetic approach
allows us to make several biaryl compounds bearing
different substituents at the corresponding position. Conse-
quently, further transformation of the functional groups in
the coupled products, R1 or R2, should furnish several 1,8-
disubstituted arylnaphthalene derivatives, and these results
will be discussed below.
2.2. Preparation of 1-aryl-substituted
8-methoxynaphthalene derivatives
8-Methoxy-1-naphthylboronic acid (1), which was readily
prepared according to the procedure in literature,9j was a
common starting material in the present synthesis of peri-
functionalized biaryl molecules. First, different reaction
conditions were examined to obtain a high chemical yield in
Suzuki–Miyaura coupling reactions of 1 with 1-haloge-
nated naphthalene derivatives (Table 1). The cross-coupling
reaction of 1-bromonaphthalene (2) with 1 for 3.5 h in the
presence of 1 mol% of Pd(PPh3)4 and Na2CO3 in DME/H2O
(6:1) at 100 8C gave 49c in a satisfactory chemical yield of
94% (entry 2). In contrast, only a trace amount of the
coupled product 4 was obtained in the absence of H2O
(entry 1) and a similar tendency was observed in the cross-
coupling reaction using Cs2CO3 as a base (entries 3 and 4).
The coupled product 4 was also prepared in excellent
chemical yield with a mixed solvent system of toluene/
EtOH/H2O (3:3:2) (entry 5). In the coupling reaction using
1-iodonaphthalene (3) as a coupling partner for 1, the
addition of H2O had positive effects, as shown in entries 7, 9
ˇ
ligands, were recently reviewed by Kocovsky and co-
workers.10 Despite the progress regarding 1,10-binaphthyl
systems as chiral inducers, less attention has been paid to the
preparation and use of the corresponding 1-aryl systems,
which are substituted by monocyclic aromatic rings.
Generally, the preparation of these compounds is based on
the Pd-mediated Suzuki–Miyaura coupling procedure,11
which has been frequently used to prepare biaryl molecular
systems. Thus, using 8-substituted naphthylboronic acid and
ortho-substituted aryl halide, the preparative approach is
Table 1. The conditions for the Suzuki–Miyaura coupling reactions
Entry
Naphthyl halide
Base
Solvent
Yield (%)
1
2
3
4
5
6
7
8
9
10
2
2
2
2
2
3
3
3
3
3
Na2CO3
Na2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Na2CO3
Na2CO3
Cs2CO3
Cs2CO3
Cs2CO3
DME
DME/H2O (6:1)
DME
DME/H2O (6:1)
Toluene/EtOH/H2O (3:3:2)
DME
DME/H2O (6:1)
DME
DME/H2O (6:1)
Toluene/EtOH/H2O (3:3:2)
Trace
94
29
99
96
Trace
55
Trace
93
98

S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
Table 2. The Suzuki–Miyaura coupling to aryl naphthalenes
2227
Entry
1
Aryl bromide (5)
Base (equiv.)
Cs2CO3 (1.5)
Pd(PPh3)4 (mol%)
Solvent systema
Yield (%)b
Product (6)
5.0
A
83
6a
2
Cs2CO3 (1.5)
5.0
A
67
6b
3
4
5
6
7
8
9
Cs2CO3 (1.5)
Cs2CO3 (1.5)
Na2CO3 (3.0)
K3PO4 (3.0)
Cs2CO3 (1.5)
CsF (1.4)
10
10
A
A
B
B
A
C
A
A
98
97c
6c
6d
6e
6f
5.0
5.0
3.0
10
63
,100
,100
43d
6g
6h
6i
Cs2CO3 (1.5)
Cs2CO3 (1.5)
5.0
10
82c
10
66
6j
a
Solvent system A: DME/H2O (6:1), B: toluene/EtOH/H2O (3:3:2), C: DME
Isolated yield.
The reaction was carried out for 24 h.
b
c
d
The reaction was carried out for 36 h at 85 8C.
and 10. With a relatively sterically hindered boronic acid,
such as peri-disubstituted naphthylboronic acid 1, as a
coupling partner, the addition of H2O as a co-solvent
dramatically promoted the coupling reaction to give the
product in improved yield. Generally, in the presence of
H2O, the coupling reactions proceeded smoothly to give 4 in
satisfactory chemical yield with either 1-bromo- or
1-iodonaphthalene as a starting 1-halogenated naphthalene.
10 mol%) for the purpose of acceleration of the reaction and
achievement of high yield, several 8-aryl-substituted
1-methoxynaphthalene derivatives were prepared with a
variety of aryl bromides as counter partners to 1, and these
results are summarized in Table 2. The coupling reaction of
2-bromotoluene (5a) with 1 gave the product 6a in 83%
yield (entry 1) and a satisfactory result (67%) was also
obtained with biphenyl bromide 5b as a coupling partner to
1 (entry 2). The aryl bromides 5c-f, which contain
heteroatom-functionalized groups at R1, were also exam-
ined to provide the corresponding coupling products in
Next, using the established coupling conditions mentioned
above with slightly increased amounts of Pd(PPh3)4 (3–

2228
S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
rather high yields. The cross-coupling of 2-bromoanisole
(5c) with 1 afforded 6c in 98% yield (entry 3) and a
compound with a MOM protective group, 6d, was obtained
from 5d12 in 97% yield (entry 4). From the MOM-protected
2-bromobenzyl alcohol, 5e,13 the product 6e was formed in
the presence of Na2CO3 in a solvent system of toluene/
EtOH/H2O (3:3:2) in 63% yield (entry 5). The product 6f
was obtained from 2-bromonitrobenzene (5f) by use of
K3PO4 as a base in quantitative yield, whereas the same
reaction in the presence of Cs2CO3 gave only trace amounts
of 6f. A pyridyl aromatic ring (Y¼N in Fig. 1) was also
successfully introduced into the biaryl framework in almost
quantitative yield (entry 7). In this case, the same solvent
system as in entries 1–4 was effective when Cs2CO3 was
used as a base. Incorporation of an ester functionality into
the 1-substituted phenyl ring was achieved by using methyl
2-bromobenzoate (5h) as a coupling partner to give 6h in
moderate yield (entry 8). The reaction conditions of CsF as a
base and single solvent system of DME were employed to
avoid the hydrolysis of ester group in this case. Despite the
significant steric hindrance of 1,2-dibromobenzene (5i), the
coupling reaction gave 6i as a sole isolable product in high
yield without any side-products derived from multiple-
coupling reactions (entry 9). The novel 2,80-dimethoxy-1,10-
binaphthalene (6j) was prepared from 5j14 in this way
(entry 10).
2.3. Further chemical transformations of 1-aryl-
substituted 8-methoxynaphthalene derivatives
With the desired Pd-mediated Suzuki–Miyaura coupling
products of 1,8-disubstituted naphthalene derivatives in
hand, the transformation of the original functional groups in
the products was examined, and these transformations are
shown in Scheme 1.
Compound 6c bearing two methoxy groups at both the
ortho-position of the 1-aryl ring and the peri-position on the
naphthalene ring system (C1 position) was treated with
BBr3 in CH2Cl2 to give dihydroxy biaryl compound 7 in
90% yield. Preliminary experiments using this compound as
a ligand showed that diol 7 can act as an effective catalyst
system with an aluminum compound for catalytic Meer-
wein–Ponndorf–Verley reduction,4c,15 and these results
will be described elsewhere. On the other hand, the
compound 6d was converted to 8, which will be considered
Scheme 1. Transformations of 1-aryl substituted 8-methoxynaphthalenes. Reagents and conditions: (a) BBr3, CH2Cl2, 215 8C to rt, 24 h, 90%; (b) conc. HCl,
MeOH, rt, 92%; (c) 6 N HCl, MeOH, reflux, 73%; (d) In, conc. HCl, THF, H2O, rt, 41 h, 93%; (e) HCHO (1.0 equiv.), NaBH3CN (1.0 equiv.), AcOH, CH3CN,
rt, 2 h, 22%; (f) HCHO (3.0 equiv.), NaBH3CN (3.0 equiv.), AcOH, CH3CN, rt, 2 h, 53%; (g) LiOH, MeOH, H2O, 80 8C, 30 h, 82%.

S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
2229
analytical conditions for complete separation of two
enantiomeric peaks corresponding to each atropisomer in
HPLC were established, and then fractions of each peak
were collected to give two kinds of fractions that contained
each enantiomer as a major component. The separation
conditions in HPLC analyses are shown in the Section 4
(Table 4). Immediately after these fractions were collected,
their optical purity was measured and then they were
allowed to stand for various length of time at ambient
temperature in a solution of the eluent solvent system
(hexane/2-propanol). These fractions were re-injected under
the same HPLC conditions after an appropriate time to
examine the degree of racemization, and the results are
shown in Table 3. Among the biaryl compounds syn-
thesized, compound 6i retained most of its original peak
even after standing for a long time, suggesting that the
energy barrier for rotation around the biaryl axis is relatively
high. Clean atropisomerization may be deduced from the
expected large steric repulsion between the ortho-substi-
tuent (Br) on the phenyl ring and the peri-position of the
naphthyl moiety (methoxy group at C1). However, re-
injection of the collected fractions of other compounds that
had been allowed to stand for 0.5 to 71 h exhibited
significant racemization even at room temperature. Prelimi-
nary experimental results indicated that the phosphine oxide
14 also partially racemized after standing 7 h at room
temperature. On the other hand, the separated each
enantiomer of newly prepared binaphthyl 6j was optically
stable after standing at ambient temperature for 71 h. The
CD spectra of each enantiomer of 6j were shown in Figure 2.
The typical positive and negative Cotton effects of isomers
indicated aR and aS configuration, respectively.18
Scheme 2. Chemical transformation to the phosphine oxide 14.
as a monodentate ligand in a future study. The treatment of
6e with the same protective group under similar conditions
gave benzyl alcohol 9 in 73% yield. Reduction of the
nitrogen functionality in the biaryl 6f with In16 in aqueous
HCl yielded the amine 10, which was further transformed
into the monomethylamino and dimethylamino derivatives,
11 and 12, through reductive amination in respective yields
of 22 and 53%. A biaryl compound with a carboxyl group 13
was obtained by alkaline hydrolysis of 6h. The bromo-
substituted biaryl 6i, which is expected to be a useful
intermediate for a variety of compounds by appropriate
further chemical transformations, was converted to the
phosphine oxide 14 in 59% yield via the halogen–metal
exchange reaction with tert-BuLi and subsequent treatment
with diphenylphosphinic chloride. Preliminary investi-
gations showed that the reduction of phosphine oxide 14
successfully proceeded to give phosphine, which acts as an
effective monodentate phosphine ligand for the Pd-mediated
intramolecular amidation reactions17 of aryl halides
(Scheme 2).
2.4. Optical behavior of synthesized biaryls
Consequently, the results of these preliminary investi-
gations suggest that an additional sp3-hybridized anchoring
group or bulky group at the 2- and/or 20-position may be
needed to slow atropisomerization in these systems.
Detailed studies of the optical behavior of the newly
synthesized compounds including kinetic experiments on
racemization will be reported elsewhere in the near future.
To evaluate their potencies as effective chiral inducers, a
preliminary examination of the optical behavior of several
newly synthesized 1,8-disubstituted naphthalene derivatives
was carried out. Thus, HPLC analysis on a chiral stationary
phase was performed to check whether or not these newly
synthesized biaryl compounds exist as a stable axially chiral
atropisomer at ambient temperature. First, the satisfactory
Table 3. The optical behavior of the synthesized biarylsa
Biaryls
Atropisomer
Ab or Bc
Optical purity (%ee) after (h)
0.25
0.5
2.0
5.0
7.0
22
24
25
41
60
71
6ad
6b
6c
A
B
A
B
A
B
89
94
86
62
54
57
39
41
28
31
26
17
18
62
8
26
2
11
6h
6i
A
B
A
B
A (S)
B (R)
A
82
94
99
,100
,100
,100
,100
,100
17
27
99
97
4
12
89
93
,100
,100
6je
14f
,100
,100
,100
,100
,100
,100
84
78
B
a
The samples were kept in 1% of 2-propanol in hexane at room temperature. See Section 4.
The atropisomer of the shorter retention time.
The atropisomer of the longer retention time.
The samples were kept in toluene at room temperature.
The samples were kept in 0.5% of 2-propanol in hexane at room temperature.
The samples were kept in 8% of 2-propanol in hexane at room temperature.
b
c
d
e
f

2230
S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
Figure 2. CD and UV spectra of (S)- and (R)-6j in MeOH (a) (R)-6j (95% ee); (b) (S)-6j (58% ee); (c) UV spectrum of (R)-6j.
3. Conclusion
4.2. General procedure for the Suzuki–Miyaura
coupling reaction with 8-methoxy-1-naphthylboronic
acid (1)
In summary, several biaryl derivatives consisting of
8-methoxynaphthalene substituted by a monocyclic aryl
ring at C1 were prepared based on the Pd-mediated Suzuki–
Miyaura coupling. Since the key structural unit of the
synthesized compounds is a peri-substituted naphthalene
ring, atropisomerization may be expected, and this possi-
bility was supported by preliminary experiments. Since
some of these compounds are expected to act as mono-
dentate or bidentate ligands for catalysts in specific
reactions, easy access to these compounds may lead to the
development of efficient chiral or non-chiral ligands by
additional fine-tuning of the molecular structure. The
application of these compounds in reactions as effective
monodentate or bidentate ligands, including asymmetric
transformation, is under investigation.
To a mixture of 8-methoxy-1-naphthylboronic acid (1)9j
(1.1 equiv.), aryl halide (1.0 equiv.) and base (1.4, 1.5 or
3.0 equiv.) in DME/H2O (6:1) or toluene/EtOH/H2O (3:3:2)
or DME was added Pd(PPh3)4 (3–10 mol%). The resulting
mixture was heated for 3.5 h at 100 8C with stirring except
for the preparation of 6d,h and j. The mixture was cooled to
room temperature and diluted with EtOAc (10 mL), then
added by H2O (10 mL). The organic layers were separated
and aqueous phase was extracted three times with EtOAc
(20 mL). The combined organic layers were dried, con-
centrated, and subjected to column chromatography on
silica gel with appropriate solvent system indicated below.
4.2.1. 8-Methoxy-1,10-binaphthalene (4). According to the
general procedure, the coupling reaction of 1-bromo-
naphthalene (2, 50 mg, 0.24 mmol) with 1 (54 mg,
0.27 mmol) was carried out in DME/H2O (6:1). After
purification by flash column chromatography (EtOAc/
hexane, 1:30), the titled compound 4 (68 mg, 99%) was
4. Experimental
4.1. General
Unless otherwise specified, all 1H NMR spectra were taken
at 270 MHz in CDCl3 with chemical shifts being reported as
d ppm from tetramethylsilane as an internal standard, and
couplings are expressed in hertz. 13C NMR spectra were
measured at 68 MHz in the same solvent. THF and ether
were distilled from sodium benzophenone ketyl, CH2Cl2
and MeOH were from calcium hydride and magnesium,
respectively. Unless otherwise noted, all reactions were run
under an argon atmosphere. All extractive organic solutions
were dried over anhydrous MgSO4, filtered and then
concentrated under reduced pressure. Column chromato-
graphy was carried out with silica gel 60 spherical (150–
325 mesh), and silica gel 60 F254 plates (Merck) were used
for preparative TLC (pTLC). HPLC analyses were
performed on the two types of analytical columns
(0.46£25 cm in size) with chiral stationary phase under
the conditions indicated in Table 4.
Table 4. The HPLC conditions for separation of each atropisomera
Biaryls
Columnb
Retention time (min)
t1 t2
Flow rate
(mL/min)
6a
6b
6c
6h
Chiralcel OD-H
Chiralcel OD-H
Chiralcel OD-H
Chiralcel OD-H
6.5
16.5
6.9
14.9
7.8
12.4
10.9 (S)
29.7
7.3
0.5
0.5
1.0
0.5
1.0
0.5
1.0
1.0
19.5
10.2
17.0
9.2
15.0
12.9 (R)
38.4
6i
Chiralcel OD-H
Chiralcel OD-H
Chiralpak AD
6jc
14d
a
A solvent system of 1% of 2-propanol in hexane was used as eluent.
Daicel Chemical. Co. LTD.
A solvent system of 0.5% of 2-propanol in hexane was used as eluent.
A solvent system of 8.0% of 2-propanol in hexane was used as eluent.
b
c
d

S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
2231
obtained as colorless solids, whose spectroscopic data were
identical with those of the authentic sample.9c
4.95–4.88 (m, 2H), 3.45 (s, 3H), 3.14 (s, 3H); 13C NMR d
156.9, 154.7, 136.1, 135.4, 135.2, 129.6, 128.5, 127.6,
127.4, 125.7, 125.5, 124.5, 121.1, 120.9, 113.9, 105.7, 94.7,
55.6, 55.4; MS (FAB) m/z 295 (MþH)þ. Anal. calcd for
C19H18O3: C, 77.53; H, 6.16. Found: C, 77.11; H, 6.11.
4.2.2. 8-Methoxy-1-(o-tolyl)naphthalene (6a). Following
the general procedure described above, the coupling
reaction of 2-bromotoluene (5a, 77 mg, 0.45 mmol) with 1
(100 mg, 0.50 mmol) was carried out in DME/H2O (6:1).
After purification by flash column chromatography on silica
gel (EtOAc/hexane, 5:95), the titled compound 6a (93 mg,
83%) was obtained as a colorless oil: Rf¼0.60 (EtOAc/
4.2.6. 8-Methoxy-1-(20-methoxymethoxymethylphenyl)-
naphthalene (6e). Following the general procedure
described above, the coupling reaction of 1-bromo-2-
methoxymethoxymethylbenzene (5e,13 91 mg, 0.39 mmol)
with 1 (88 mg, 0.43 mmol) was carried out in toluene/EtOH/
H2O (3:3:2). After purification by flash column chromato-
graphy (EtOAc/hexane, 1:9), the titled compound 6e
(77 mg, 63%) was obtained as a colorless oil: Rf¼0.60
1
hexane, 5:95); H NMR d 7.79 (d, J¼8.4 Hz, 1H), 7.50–
7.38 (m, 2H), 7.36–7.24 (m, 1H), 7.19–7.15 (m, 5H), 6.72
(d, J¼7.6 Hz, 1H), 3.41 (s, 3H), 1.95 (s, 3H); 13C NMR
d156.8, 145.3, 138.2, 135.8, 135.5, 128.21, 128.16, 128.09,
127.4, 126.0, 125.8, 125.6, 124.4, 124.0, 121.2, 105.7, 55.4,
20.1; MS (FAB) m/z 249 (MþH)þ; HRMS calcd for
C18H16O (Mþ) 248.1201, found 248.1196. Anal. calcd for
C18H16O: C, 87.06; H, 6.49. Found: C, 86.75; H, 6.22.
1
(EtOAc/hexane, 1:9). H NMR d 7.81 (d, J¼7.3 Hz, 1H),
7.51–7.16 (m, 8H), 6.73 (d, J¼7.3 Hz, 1H), 4.47–4.41 (m,
2H), 4.26 (s, 2H), 3.31 (s, 3H), 3.13 (s, 3H); 13C NMR d
154.4, 142.2, 134.4, 133.3, 133.2, 126.5, 126.2, 125.5,
124.2, 124.0, 123.9, 123.7, 123.2, 121.7, 118.9, 103.6, 93.6,
65.3, 53.1, 52.7; MS (FAB) m/z 309 (MþH)þ; HRMS calcd
for C20H20O3 (MþH)þ 309.1491, found 309.1459.
4.2.3. 8-Methoxy-1-(biphenyl-20-yl)naphthalene (6b).
According to the general procedure, the coupling reaction
of 2-bromobiphenyl (5b, 52 mg, 0.23 mmol) with 1 (50 mg,
0.25 mmol) was carried out in DME/H2O (6:1). After
purification by flash column chromatography (EtOAc/
hexane, 5:95), the titled compound 6b (47 mg, 67%) was
obtained as a colorless oil: Rf¼0.70 (EtOAc/hexane, 1:9);
1H NMR d 7.59 (d, J¼7.9 Hz, 1H), 7.34–7.15 (m, 7H),
7.04–6.90 (m, 6H), 6.55 (d, J¼7.3 Hz, 1H), 3.39 (s, 3H);
13C NMR d 156.3, 143.9, 142.0, 140.0, 138.0, 135.3, 129.7,
129.34, 129.27, 128.8, 127.3, 127.1, 126.3, 125.8, 125.71,
125.66, 125.2, 124.3, 120.8, 105.1, 55.0; MS (FAB) m/z 311
(MþH)þ; HRMS calcd for C23H18O (Mþ) 310.1358, found
310.1350. Anal. calcd for C23H18O: C, 89.00; H, 5.85.
Found: C, 88.56; H, 5.46.
4.2.7. 8-Methoxy-1-(20-nitrophenyl)naphthalene (6f).
Following the general procedure described above, the
coupling reaction of 1-bromo-2-nitrobenzene (5f, 44 mg,
0.22 mmol) with 1 (48 mg, 0.24 mmol) was peRformed in
toluene/EtOH/H2O (3:3:2). After purification by flash
column chromatography (EtOAc/hexane, 1:9), the titled
compound 6f (64 mg, quantitative) was obtained as yellow
1
solids; Rf¼0.70 (EtOAc/hexane, 1:9); mp 102–104 8C; H
NMR d 8.10–8.06 (m, 1H), 7.86–7.82 (m, 1H), 7.61–7.33
(m, 6H), 7.24–7.20 (m, 1H), 6.72 (d, J¼7.6 Hz, 1H), 3.44
(s, 3H); 13C NMR d 155.8, 148.6, 140.7, 135.2, 134.5,
131.8, 131.7, 128.4, 128.2, 127.4, 127.0, 126.1, 125.5,
123.1, 121.4, 105.6, 55.2; MS (FAB) m/z 280 (MþH)þ.
Anal. calcd for C17H13NO3: C, 73.12; H, 4.66; N, 5.02.
Found: C, 72.93; H, 4.78; N, 4.94.
4.2.4. 8-Methoxy-1-(20-methoxyphenyl)naphthalene (6c).
Following the general procedure described above, the
coupling reaction of 2-bromoanisole (5c, 841 mg,
4.50 mmol) with 1 (1.0 g, 4.95 mmol) was carried out in
DME/H2O (6:1). After purification by flash column
chromatography (toluene/hexane, 1:3), the titled compound
6c (1.17 g, 98%) was obtained as a colorless oil; Rf¼0.55
4.2.8. 80-Methoxy-10-(3-methylpyridin-2-yl)naphthalene
(6g). Following the general procedure described above,
the coupling reaction of 2-bromo-3-methylpyridine (5g,
39 mg, 0.23 mmol) with 1 (50 mg, 0.25 mmol) was carried
out in DME/H2O (6:1). After purification by flash column
chromatography (EtOAc/hexane, 1:5), the titled compound
6g (67 mg, quantitative) was obtained as a colorless oil;
Rf¼0.45 (EtOAc/hexane, 1:5); 1H NMR d 7.77 (dd, J¼1.0,
7.2 Hz, 1H), 7.46–7.40 (m, 3H), 7.32–7.27 (m, 1H), 7.20–
7.17 (m, 1H), 7.08 (dd, J¼2.6, 4.9 Hz, 1H), 6.66 (d,
J¼7.6 Hz, 1H), 3.36 (s, 3H), 1.90 (s, 3H); 13C NMR d 162.4,
155.8, 144.8, 136.6, 135.5, 135.1, 131.1, 127.7, 126.8,
125.6, 125.4, 123.0, 121.0, 120.4, 105.3, 55.1, 18.9; MS
(FAB) m/z 251 (MþH)þ; HRMS calcd for C17H15NO (Mþ)
250.1239, found 250.1232.
1
(EtOAc/hexane, 1:7); H NMR d 7.79 (dd, J¼1.3, 6.9 Hz,
1H), 7.50–7.44 (m, 2H), 7.39–7.18 (m, 4H), 7.01–6.95 (m,
1H), 6.88 (d, J¼8.3 Hz, 1H), 6.76–6.72 (m, 1H), 3.63 (s,
3H), 3.46 (s, 3H); 13C NMR d 157.12, 157.07, 135.4, 135.3,
135.0, 129.5, 128.6, 127.7, 127.5, 125.7, 125.6, 124.6,
121.2, 119.6, 109.4, 106.0, 55.5; MS (FAB) m/z 265
(MþH)þ; HRMS calcd for C18H16O2 (Mþ) 264.1150, found
264.1163. Anal. calcd for C18H16O2: C, 81.79; H, 6.10.
Found: C, 81.48; H, 6.06.
4.2.5. 1-(2-Methoxymethoxyphenyl)-8-methoxynaphtha-
lene (6d). According to the general procedure, the coupling
reaction of methoxymethyl 2-bromophenyl ether (5d,12
99 mg, 0.46 mmol) with 1 (111 mg, 0.55 mmol) was carried
out at 100 8C for 24 h in DME/H2O (6:1). After purification
by pTLC with the developing solvent (EtOAc/hexane, 1:5),
the titled compound 6d (130 mg, 97%) was obtained as
white brown solids: Rf¼0.36 (EtOAc/hexane, 1:5); mp 71–
4.2.9. 8-Methoxy-1-(20-methoxycarbonylphenyl)-
naphthalene (6h). To a mixture of methyl 2-bromobenzo-
ate (5h, 100 mg, 0.47 mmol), 1 (113 mg, 0.56 mmol) and
CsF (99 mg, 0.65 mmol) in DME (4.0 mL) was added
Pd(PPh3)4 (54 mg, 0.047 mmol) and the mixture was stirred
for 36 h at 85 8C. The mixture was added by H2O and
EtOAc, and then filtered through Celite pad. The filtrate was
extracted with EtOAc and the extracts were washed, dried
and concentrated to give a residue, which was subjected to
1
73 8C; H NMR d 7.79 (d, J¼8.2 Hz, 1H), 7.49–7.43 (m,
2H), 7.39–7.30 (m, 1H), 7.28–7.18 (m, 3H), 7.12 (d,
J¼7.9 Hz, 1H), 7.06–7.00 (m, 1H), 6.73 (d, J¼7.6 Hz, 1H),

2232
S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
flash column chromatography on silica gel with EtOAc/
hexane (1:30) to give crude product. Purification by pTLC
of the crude sample with EtOAc/hexane (1:7) gave the titled
compound 6h (58 mg, 43%) as colorless solids; Rf¼0.44
(EtOAc/hexane, 1:7); mp 78–80 8C; 1H NMR d 7.99–7.96
(m, 1H), 7.80 (d, J¼7.6 Hz, 1H), 7.52–7.26 (m, 7H), 7.17
(dd, J¼1.0, 5.9 Hz, 1H), 6.71 (d, J¼7.6 Hz, 1H), 3.42 (s,
3H), 3.36 (s, 3H); 13C NMR d 167.4, 155.9, 146.1, 137.9,
134.6, 130.1, 129.8, 129.6, 128.4, 127.0, 126.8, 125.5,
125.2, 124.9, 123.3, 120.8, 105.1, 54.7, 51.0; MS (FAB) m/z
293 (MþH)þ; HRMS calcd for C19H16O3 (MþH)þ
293.1177, found 293.1131. Anal. calcd for C19H16O3: C,
78.06; H, 5.52. Found: C, 77.78; H, 5.63.
to warm to room temperature for 21 h, and then added with
MeOH at 0 8C. After being stirred for 10 min at the same
temperature, 1 N HCl (3.0 mL) and conc.NH4OH were
successively added to the mixture, and the mixture was
extracted with CHCl3. The combined organic extracts were
dried and concentrated to give the residue, from which the
titled compound 7 (160 mg, 90%) was obtained as white
brown solids; Rf¼0.83 (EtOAc/hexane, 1:9); mp 65–69 8C;
1H NMR d 7.93 (d, J¼8.3 Hz, 1H), 7.54–7.30 (m, 6H), 7.10
(d, J¼8.1 Hz, 2H), 6.93 (d, J¼7.6 Hz, 1H), 5.74 (s, 1H),
5.02 (s, 1H); 13C NMR d 153.4, 153.1, 136.0, 131.0, 130.3,
129.9, 129.8, 129.5, 129.3, 129.1, 127.2, 126.6, 125.3, 121.1,
116.3, 112.1; MS (FAB) m/z 237 (MþH)þ; HRMS calcd for
C16H12O2 (Mþ) 236.0837, found 236.0832. Anal. calcd for
C16H12O2: C, 81.34; H, 5.12. Found: C; 80.92; H, 5.50.
4.2.10. 8-Methoxy-1-(20-bromophenyl)naphthalene (6i).
Following the general procedure, the coupling reaction of
1,2-dibromobenzene (5i, 106 mg, 0.45 mmol) with 1
(100 mg, 0.50 mmol) was carried out in DME/H2O (6:1).
After purification by flash column chromatography (EtOAc/
hexane, 1:98 to 2:98), the titled compound 6i (115 mg, 82%)
was obtained as a colorless oil; Rf¼0.50 (EtOAc/hexane,
2:98); 1H NMR d 7.84 (d, J¼8.2 Hz, 1H), 7.59 (d,
J¼7.6 Hz, 1H), 7.51–7.14 (m, 6H), 3.76 (d, J¼7.6 Hz,
1H), 3.49 (s, 3H); 13C NMR d 156.5, 146.2, 137.5, 135.2,
131.0, 129.8, 129.6, 128.1, 127.4, 126.0, 125.4, 123.8,
123.7, 121.1, 105.9, 55.6; MS (FAB) m/z 315 (MþH)þ;
HRMS calcd for C17H13BrO (Mþ) 314.0129, found
314.0137. Anal. calcd for C17H13BrO: C, 65.19; H, 4.18.
Found: C, 65.41; H, 4.20.
4.2.13. 8-Methoxy-1-(20-hydroxyphenyl)naphthalene (8).
To a stirred solution of 6d (130 mg, 0.44 mmol) in MeOH
(5.2 mL) was added conc.HCl (0.26 mL), and the mixture
was stirred for 5.7 h at room temperature. Concentration of
the mixture followed by purification by flash column
chromatography on silica gel with EtOAc and hexane
(1:15 to 1:7) furnished the titled compound 8 (102 mg, 92%)
as white brown solids; Rf¼0.22 (EtOAc/hexane, 1:7); mp
115–117 8C; 1H NMR d 7.88 (d, J¼8.6 Hz, 1H), 7.56–7.50
(m, 2H), 7.46–7.40, (m, 1H), 7.34 (d, J¼6.9 Hz, 1H), 7.29–
7.22 (m, 1H), 7.15 (d, J¼7.8 Hz, 1H), 6.98–6.93 (m, 2H),
6.82 (d, J¼7.6 Hz, 1H), 3.53 (s, 3H); 13C NMR d 156.5,
152.7, 135.8, 132.1, 132.0, 130.1, 129.4, 129.0, 128.8,
128.0, 126.4, 126.1, 124.0, 119.5, 114.0, 106.5, 55.7; MS
(FAB) m/z 251 (MþH)þ. Anal. calcd for C17H14O2: C,
81.58; H, 5.64. Found: C; 81.07; H, 5.46.
4.2.11. 2,80-Dimethoxy-1,10-binaphthalene (6j). Accord-
ing to the general procedure, the coupling reaction of
1-bromo-2-methoxynaphthalene (5j, 107 mg, 0.45 mmol)
with 1 (100 mg, 0.50 mmol) was carried out at 100 8C for
24 h in DME/H2O (6:1). After purification by pTLC with
the developing solvent of toluene and hexane (1:2), the
titled compound 6j (93 mg, 66%) was obtained as off-white
solids: Rf¼0.41 (EtOAc/hexane, 1:7 on NH-SiO2 plate); mp
121–124 8C; 1H NMR d 7.90–7.81 (m, 3H), 7.58–7.53 (m,
2H), 7.40–7.34 (m, 2H), 7.30–7.25 (m, 2H), 7.21–7.12 (m,
1H), 6.68 (d, J¼7.6 Hz, 1H), 3.74 (s, 3H), 3.12 (s, 3H); 13C
NMR d 157.1, 153.1, 135.8, 134.0, 132.5, 129.5, 129.1,
128.6, 127.7, 127.6, 127.5, 125.8, 125.7, 125.6, 125.4,
123.0, 121.3, 114.0, 106.2, 57.0, 55.6; MS (FAB) m/z 315
(MþH)þ; HRMS calcd for C22H19O2 (MþH)þ 315.1385,
found 315.1391.
4.2.14. 8-Methoxy-1-(20-hydroxymethylphenyl)naphtha-
lene (9). To a stirred solution of 6e (77 mg, 0.25 mmol) in
MeOH (5.0 mL) was added 6 N HCl (3.0 mL) and the
mixture was refluxed overnight. The reaction mixture was
then cooled to room temperature and diluted with H2O. The
mixture was extracted with EtOAc and the organic layer
was dried and evaporated. The residue was purified by flash
column chromatography with EtOAc and hexane (1:9) to
give the titled compound 9 (48 mg, 73%) as colorless solids;
1
Rf¼0.50 (EtOAc/hexane, 1:9); mp 77–80 8C; H NMR d
7.85–7.82 (m, 1H), 7.55–7.13 (m, 8H), 6.79 (d, J¼7.6 Hz,
1H), 4.41 (d, J¼12.2 Hz, 1H), 4.32 (d, J¼12.6 Hz, 1H), 3.41
(s, 3H); 13C NMR d 156.2, 144.2, 138.0, 136.4, 135.5,
132.6, 128.9, 128.8, 128.5, 127.6, 127.0, 126.6, 126.4,
126.0, 125.5, 121.8, 107.0, 65.0; MS (FAB) m/z 265
(MþH)þ; HRMS calcd for C18H16O2 (Mþ) 264.1150, found
264.1142.
The racemic 6j was subjected to the preparative HPLC on
chiral stationary phase (Chiralcel OD-H, solvent system:
0.5% of 2-propanol in hexane, 1 mL/min) to give the
optically active enantiomers.
4.2.15. 8-Methoxy-1-(20-aminophenyl)naphthalene (10).
To a stirred mixture of 6f (470 mg, 1.68 mmol), conc.HCl
(1.2 mL), THF (3.0 mL) and H2O (9.0 mL) was added
indium (773 mg, 6.73 mmol) at room temperature, and the
resulting mixture was further stirred for 17 h at room
temperature. Additional indium (386 mg, 3.37 mmol) and
conc.HCl (0.6 mL) were added to the mixture and then
stirring was continued for additional 24 h at room
temperature. The mixture was diluted with EtOAc and
water, and then neutralized by addition of saturated aqueous
solution of NaHCO3. The mixture was filtered through a
thin pad of Celite and the filtrate was extracted with EtOAc
Compound (S)-6j. 58% ee; [a]2D0 11.0 (c 0.35, CHCl3); CD
(MeOH) lext (D1) 290.2 nm (5.3), 237.4 nm (289.3).
Compound (R)-6j. 95% ee; [a]2D0 213.3 (c 0.21, CHCl3);
CD (MeOH) lext (D1) 290.8 nm (28.2), 237.6 nm (136.8);
UV (MeOH) lmax 230.0 nm (1 66086), 296.0 nm (1 8555).
4.2.12. 8-Hydroxy-1-(20-hydroxyphenyl)naphthalene (7).
To a solution of 6c (200 mg, 0.76 mmol) in CH2Cl2
(2.0 mL) was added 1M solution of BBr3 in CH2Cl2
(2.27 mL, 2.27 mmol) at 270 8C. The mixture was allowed

S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
2233
three times and the combined organic extracts were washed,
dried and evaporated. The residue was purified by flash
column chromatography (EtOAc/hexane, 1:15) to give the
titled compound 10 (390 mg, 93%) as white brown solids;
Rf¼0.55 (Et3N/EtOAc/hexane, 1:10:90); mp 107–109 8C;
1H NMR d 7.83 (dd, J¼1.3, 6.9 Hz, 1H), 7.53–7.48 (m,
2H), 7.43–7.37 (m, 1H), 7.31–7.28 (m, 1H), 7.18–7.12 (m,
1H), 7.08–7.04 (m, 1H), 6.82–6.72 (m, 3H), 3.52 (s, 3H);
13C NMR d 143.8, 135.8, 135.3, 135.2, 133.4, 129.2, 129.0,
128.0, 127.4, 127.2, 126.1, 121.3, 117.6, 114.1, 106.6, 56.0;
MS (FAB) m/z 250 (MþH)þ; HRMS calcd for C17H15NO
(Mþ) 249.1153, found 249.1141.
mixture was heated at 80 8C with stirring for 21 h. Stirring
was further continued for 9 h after addition of additional
amount of LiOH·H2O (9.0 mg, 0.21 mmol) at the same
temperature. After cooling, the mixture was poured into 2 N
HCl and extracted with EtOAc and chloroform. The organic
phases were washed, dried and concentrated to give the
residue, which was purified by pTLC with a developing
solvent system of EtOAc, hexane and AcOH (30:60:0.9) to
give the titled compound 13 (31 mg, 82%) as colorless
solids; mp 181–185 8C; 1H NMR d 8.03–7.99 (m, 1H), 7.80
(d, J¼7.8 Hz, 1H), 7.53–7.23 (m, 6H), 7.16 (d, J¼6.8 Hz,
1H), 6.70 (d, J¼6.8 Hz, 1H), 3.40 (s, 3H); 13C NMR d
171.7, 156.2, 147.0, 137.9, 135.1, 131.1, 130.5, 129.4,
128.9, 127.5, 127.3, 126.0, 125.6, 125.3, 123.7, 121.2,
105.6, 55.1; MS (FAB) m/z 279 (MþH)þ; HRMS calcd
for C18H14O3 (Mþ) 278.0943, found 278.0929. Anal.
calcd for C18H14O3: C, 77.68; H, 5.07. Found: C, 77.59;
H, 5.42.
4.2.16. 8-Methoxy-1-(20-N-methylaminophenyl)naphtha-
lene (11). To a solution of 10 (60 mg, 0.24 mmol) in
CH3CN (10 mL) was added 37% aqueous solution of
formaldehyde (17 mL, 0.24 mmol) and AcOH (0.5 mL).
The mixture was stirred for 30 min at 0 8C, then additional
NaBH3CN (15 mg, 0.24 mmol) and AcOH (0.5 mL) were
added, and the mixture was stirred for 30 min at room
temperature. The mixture was evaporated in vacuo to afford
the residue, which was partitioned between EtOAc and 1 N
NaOH, and the organic phase was separated, and the
extraction was completed with additional portion of EtOAc.
The combined extracts were dried and evaporated to give
the residue, which was purified by pTLC (Et3N/EtOAc/
hexane, 1:10:90). The titled compound 11 (14 mg, 22%)
was afforded as a brown oil; Rf¼0.50 (Et3N/EtOAc/hexane,
4.2.19. 8-Methoxy-1-(20-diphenylphosphinoylphenyl)-
naphthalene (14). To
a solution of 6i (153 mg,
0.49 mmol) in dry Et2O (10 mL) at 278 8C was added
dropwise tert-BuLi (0.33 mL, 0.54 mmol), and the mixture
was stirred for 1 h at the same temperature, and then a
solution of Ph2P(O)Cl (101 mg, 0.59 mmol) in dry Et2O
(10 mL) was added. The mixture was allowed to warm to
room temperature overnight, and then partitioned between
EtOAc and 1 N NaOH. The each phase was separated, and
the extraction was completed with additional portion of
EtOAc. The combined organic extracts were dried and
evaporated. The residue was purified by flash column
chromatography (EtOAc/hexane, 1:9 to 1:0) to give the
titled compound 14 (125 mg, 59%) as colorless solids;
1
1:10:90); H NMR d 7.84–7.81 (m, 1H), 7.48–7.43 (m,
2H), 7.39 (t, J¼8.2 Hz, 1H), 7.30–7.20 (m, 2H), 7.02 (dd,
J¼1.6, 5.7 Hz, 1H), 6.80–6.73 (m, 2H), 6.66 (d, J¼8.1 Hz,
1H), 3.49 (s, 3H), 2.72 (s, 3H); 13C NMR d 156.9, 146.9,
135.9, 135.1, 131.8, 129.5, 128.0, 127.4, 126.2, 126.0,
121.3, 115.9, 108.6, 106.5, 55.8, 31.0; MS (FAB) m/z 264
(MþH)þ; HRMS calcd for C18H17NO (Mþ) 263.1311,
found 263.1320. Anal. calcd for C18H17NO: C, 81.10; H,
6.51; N, 5.32. Found; C, 80.76; H, 6.51; N, 5.05.
1
Rf¼0.10 (EtOAc); mp 132–135 8C; H NMR d 7.81–7.72
(m, 1H), 7.54–7.32 (m, 7H), 7.25–6.96 (m, 11H), 6.47
(m, 1H), 3.41 (s, 3H); MS (FAB) m/z 435 (MþH)þ;
HRMS calcd for C29H24OP (MþH)þ; 435.1643, found
435.1630.
4.2.17. 8-Methoxy-1-(20-N,N-dimethylaminophenyl)-
naphthalene (12). Following the procedure for the
preparation of 11, to a mixture of 10 (37 mg, 0.15 mmol),
CH3CN (0.5 mL) and 37% aqueous formaldehyde solution
(32 mL, 0.45 mmol) was successively added NaBH3CN
(28 mg, 0.45 mmol) and AcOH (1.0 mL) at 0 8C. After the
mixture was stirred for 1 h at 0 8C, additional AcOH
(1.0 mL) was added to the mixture, which was stirred for
18 h at room temperature and worked up in a similar way to
that described above to give the residue, from which the
titled compound 12 (22 mg, 53%) was obtained as a brown
oil after purification by pTLC (Et3N/EtOAc/hexane,
1:10:90); Rf¼0.60 (Et3N/EtOAc/hexane, 1:10:90); 1H
NMR d 7.76 (d, J¼8.1 Hz, 1H), 7.48–7.44 (m, 2H),
7.39–7.22 (m, 3H), 7.10–6.92 (m, 3H), 6.73 (d, J¼7.6 Hz,
1H), 3.47 (s, 3H), 2.42 (s, 6H); 13C NMR d 156.9, 151.0,
138.7, 138.0, 135.8, 130.6, 128.8, 127.0, 126.8, 125.7,
125.6, 124.0, 121.0, 120.3, 116.9, 105.3, 45.7, 43.3; MS
(FAB) m/z 278 (MþH)þ; HRMS calcd for C19H20NO
(MþH)þ 278.1545, found 278.1540.
References and notes
1. (a) Ojima, I. Catalytic asymmetric synthesis; Wiley: New
York, 1993. (b) In Asymmetric catalysis in organic synthesis;
Noyori, R., Ed.; Wiley: New York, 1994. (c) Seyden-Penne, J.
Chiral auxiliaries and ligands in asymmetric synthesis; Wiley:
New York, 1995.
2. (a) Miyashita, A.; Yasuda, A.; Takaya, H.; Toriumi, K.; Ito, T.;
Souchi, T.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 7932. (b)
Takaya, H.; Akutagawa, S.; Noyori, R. Org. Synth. 1988, 67,
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3. (a) Uozumi, Y.; Hayashi, T. J. Am. Chem. Soc. 1991, 113,
9887. (b) Hayashi, T.; Hirate, S.; Kitayama, K.; Tsuji, H.;
Torii, A.; Uozumi, Y. J. Org. Chem. 2001, 66, 1441. For
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Svenstrup, N.; Robertson, M.; Jørgensen, K. A. Chem. Eur. J.
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Angew. Chem., Int. Ed. Engl. 2002, 41, 1020. (d) Shibasaki,
M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187.
4.2.18. 8-Methoxy-1-(20-carboxyphenyl)naphthalene
(13). To a stirred mixture of 6h (40 mg, 0.14 mmol),
MeOH (4.0 mL) and water (1.0 mL) was added LiOH·H2O
(9.0 mg, 0.21 mmol) at room temperature and the reaction

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S. Yoshikawa et al. / Tetrahedron 60 (2004) 2225–2234
5. (a) Fuji, K.; Kawabata, T.; Kuroda, A. J. Org. Chem. 1995, 60,
(m) Iovine, P. M.; Kellett, M. A.; Redmore, N. P.; Therien,
M. J. J. Am. Chem. Soc. 2000, 122, 8717. (n) Fukui, H.;
Fukushi, Y.; Tahara, S. Tetrahedron Lett. 2003, 44, 4063. (o)
Zhang, S.-W.; Swager, T. M. J. Am. Chem. Soc. 2003, 125,
3420.
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