An efficient catalyst for the synthesis of ortho-substituted biaryls by the Suzuki cross-coupling: Triphenylphosphine adduct of cyclopalladated ferrocenylimine

Article abstract of DOI:10.1016/j.jorganchem.2006.09.023

The air and moisture stable triphenylphosphine adduct of cyclopalladated ferrocenylimine 2 has been successfully used in palladium-catalyzed Suzuki cross-coupling for the synthesis of ortho-substituted biaryls in air. In the presence of 0.05 mol% of 2 as catalyst and 3 equivalent of CsF as base in dioxane at 100 °C, ortho-substituted biaryls were synthesized with moderate to high yields in the reactions of 2-methoxy-1-naphthylboronic acid with aryl halides, and 14 new ortho-substituted biaryls were obtained and characterized.

Full text of DOI:10.1016/j.jorganchem.2006.09.023

Journal of Organometallic Chemistry 691 (2006) 5688–5696
www.elsevier.com/locate/jorganchem
An efficient catalyst for the synthesis of ortho-substituted biaryls
by the Suzuki cross-coupling: Triphenylphosphine adduct of
cyclopalladated ferrocenylimine
*
Hong Li, Yangjie Wu , Weibo Yan
Department of Chemistry, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan
Universities, Zhengzhou University, Zhengzhou 450052, PR China
Received 27 July 2006; received in revised form 26 August 2006; accepted 14 September 2006
Available online 19 September 2006
Abstract
The air and moisture stable triphenylphosphine adduct of cyclopalladated ferrocenylimine 2 has been successfully used in palladium-
catalyzed Suzuki cross-coupling for the synthesis of ortho-substituted biaryls in air. In the presence of 0.05 mol% of 2 as catalyst and 3
equivalent of CsF as base in dioxane at 100 ꢀC, ortho-substituted biaryls were synthesized with moderate to high yields in the reactions of
2-methoxy-1-naphthylboronic acid with aryl halides, and 14 new ortho-substituted biaryls were obtained and characterized.
ꢁ 2006 Elsevier B.V. All rights reserved.
Keywords: Cyclopalladated ferrocenylimine; Triphenylphosphine adduct; ortho-Substituted biaryls; Suzuki coupling; 2-Methoxy-1-naphthylboronic acid
1. Introduction
heteroatom bond formation and have attracted much
attention owning to their availability, facile modification,
insensitivity to air or moisture and easy handling as com-
pared with the most other catalysts [7]. However, only in
rare cases Suzuki couplings of sterically hindered substrates
have been investigated with palladacycles. Bedford et al.
reported recently that phosphinito-based palladacycles in
the presence of PCy3 were efficient catalysts for the Suzuki
coupling of sterically hindered substrates [8].
Although many palladacycles have been reported for
Suzuki coupling, there are no large difference in catalyst
activity because they generate a ligand-free nanoparticles
as active species for oxidative addition of haloarenes[9].
Our laboratory has been focusing on the studies of cyclo-
metallation of ferrocenylimines and their applications [10].
We found that cyclopalladated ferrocenylimines, such as
1, were efficient catalysts for the Heck reaction [11], the
dimerization of arylmercurials [12], and the Suzuki coupling
reaction [13]. As an extension of our studies, we report
herein the preparation of ortho-substituted biaryls by the
Suzuki cross-coupling using 2 as palladacyclic catalyst and
2-methoxy-1-naphthylboronic acid as a hindered partner.
ortho-Substituted biaryls are important structure moie-
ties of biologically active compounds and organic func-
tional materials [1]. However, the linking of sterically
hindered carbon centers is very difficult and the formation
of ortho-substituted biaryls under mild conditions has
remained elusive [2]. Thus, a general method for the syn-
thesis of hindered biaryls has yet to be realized [3]. The
Suzuki cross-coupling is among the most powerful tools
for the construction of biaryl bonds due to its efficiency
and wide functional-group tolerance [4]. There is currently
considerable interest in the development of efficient cata-
lysts that can catalyze the Suzuki-coupling reaction to form
ortho-substituted biaryls [5,6]. Advances have been made
with efficacious supporting ligands, such as phosphines
[5] and N-heterocyclic carbenes [6] to increase the activity
of catalysts. Moreover, palladacyclic catalysts are among
the most active catalysts for carbon–carbon and carbon-
*
Corresponding author. Tel./fax: +86 371 67979408.
E-mail address: wyj@zzu.edu.cn (Y. Wu).
0022-328X/$ - see front matter ꢁ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.09.023

H. Li et al. / Journal of Organometallic Chemistry 691 (2006) 5688–5696
5689
of 0.01 mol%, the biaryl was obtained in 47% yield (entry
10).
CH3
CH3
N
C
C
The scope of ortho-substituted Suzuki cross-coupling
was investigated by varying the aryl halides under the opti-
mized reaction conditions (CsF, dioxane, 100 ꢀC) (Table 2).
A list of electronically and structurally diverse aryl halides
including heteroaryl halides underwent the cross-coupling
reactions very efficiently with 2-methoxy-1-naphthylbo-
ronic acid.
N
CH3
CH3
Fe
Fe
Pd Cl
Pd Cl
PPh3
2
1
2
A strongly electron-donating group such as methoxy
also provided the biaryl product with a isolated yield of
94% using 0.05 mol% of 2 after 2 h (entries 1–3). The use
of 4-N-dimethylphenyl bromide led to a drop in isolated
yield under the same amount of catalyst after 6 h (63%,
entry 4). The difference in the yield could be easily
explained by the difference in electron-donating capability.
For activated bromides such as 4-bromonitrobenzene, 4-
bromobenzonitrile and 4-bromobenzotrifluoride, yields of
99%, 94% and 99% were obtained respectively (entries 7,
9, 10). For catalyst 2, no great activity loss was observed
even when the catalyst loading was reduced to 0.01 mol%
in the reaction of activated bromides with 2-methoxy-1-
naphthylboronic acid (entry 8).
When ortho-substituents were used in the reactions, the
ortho-monosubstituted aryl bromides, such as 2-methyl-
bromobenzene gave high product yield (entry 12). In
contrast, when the ortho-disubstituted aryl bromides were
used, such as 2-bromo-m-xylene, the isolated yield was
dropped to 22% (entry 13).
2. Results and discussion
Initially, the Suzuki cross-coupling reactions of 4-meth-
oxylphenyl bromide with 2-methoxy-1-naphthylboronic
acid were carried out with various catalysts, bases and sol-
vents. The results were shown in Table 1. The performance
of catalyst 1 and 2 was first tested (entries 1–3), and 2
exhibited higher activity with a loading as low as
0.1 mol%. The Suzuki cross-coupling reactions were gener-
ally carried out under the protection of inert gas [3h,14].
We found that the reaction occurred smoothly in air and
afford the corresponding biaryl with similar yield (entries
1 and 2). We further investigated the effect of bases and
found that CsF was the best among the bases tested (entries
3–7). Finally, the effect of solvents was studied (entries 3,
8–10). We discovered that dioxane was better than other
solvents with a low catalyst loading of 0.05 mol% (entry
9). When the catalyst loadings were reduced to a level
Table 1
Effect of catalysts, bases and solvents on the Suzuki coupling of 4-methoxylphenyl bromide with 2-methoxy-1-naphthylboronic acid
OCH3
B(OH)2
Br
OCH3
Cat. / Base
Solvent
+
OCH3
OCH3
4
3c
5c
Entry
Cat.
Cat. (mol%)
Base
Solvent
T (ꢀC)
Time (h)
% Yielda
1b
2
3
4
5
6
7
8
1
1
2
2
2
2
2
2
2
2
1
1
CsF
CsF
CsF
DME
DME
DME
DME
DME
DME
DME
Toluene
Dioxane
Dioxane
80
80
80
80
80
80
80
110
100
100
10
10
6
6
6
6
6
6
2
62
61
86
71
39
58
52
38
94
47
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.01
K3PO4
Ba(OH)2 Æ 8 H2O
KF Æ 2H2O
Cs2CO3
CsF
9
10
CsF
CsF
6
Reaction conditions: 4-methoxylphenyl bromide (0.3 mmol), 2-methoxy-1-naphthylboronic acid (0.33 mmol), Base (0.99 mmol), Solvent (2 mL).
a
Isolated yields, based on 4-methoxylphenyl bromide, average of two runs.
Protected by N2.
b

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H. Li et al. / Journal of Organometallic Chemistry 691 (2006) 5688–5696
Table 2
Suzuki coupling of aryl halides with 2-methoxy-1-naphthylboronic acid
Ar
B(OH)2
OCH3
OCH3
Cat. 2 / CsF
dioxane /100 oC
+
ArX
5
3
4
Entry
1
ArX
Cat. 2 (mol%)
Time (h)
2
Product
No. of
products
% Yielda
97
Br
3a
0.05
5a
OCH3
Br
2
3b
0.05
2
5b
94
OCH3
Br
3
3c
0.05
2
5c
94
OCH
3
OCH
3
OCH3
Br
N
4
3d
0.05
6
5d
63
N
OCH3
Br
5
3e
0.05
2
O
5e
90
OCH
3
O
Br
Cl
6
3f
0.05
2
5f
91
Cl
OCH3
Br
7
3g
0.05
2
NO2
5g
99
OCH3
NO2

H. Li et al. / Journal of Organometallic Chemistry 691 (2006) 5688–5696
5691
Table 2 (continued)
Entry
ArX
Cat. 2 (mol%)
Time (h)
2
Product
No. of
products
% Yielda
88
Br
8
3g
0.01
NO2
5g
OCH3
NO2
9
Br
3h
0.05
2
5h
94
CN
OCH
3
CN
Br
10
3i
0.05
2
5i
99
CF3
OCH3
CHO
CF3
Br
11
3j
0.05
2
5j
95
OCH
3
CHO
Br
12
13
14
3k
0.05
0.05
0.05
2
5k
93
22
75
OCH3
Br
3l
20
5l
OCH3
Br
3m
2
5m
OCH
OCH
OCH
3
3
3
Br
15
16
3n
3o
0.1
0.1
20
5n
5o
33
78
N
N
Br
6
N
N
(continued on next page)

5692
H. Li et al. / Journal of Organometallic Chemistry 691 (2006) 5688–5696
Table 2 (continued)
Entry
ArX
Cat. 2 (mol%)
Time (h)
20
Product
No. of
products
% Yielda
71
17
3p
3q
0.1
5p
Br
S
S
OCH3
Br
18
19
0.1
0.5
20
24
5q
65
S
S
OCH3
Cl
3a
5a
Trace
OCH3
Cl
20
3e
0.5
20
5e
51
O
O
OCH
3
Cl
21
3f
0.5
6
5f
96
NO2
NO2
OCH3
Cl
22
3r
0.5
6
5r
77
NO2
NO2
OCH3
Cl
23
3s
0.5
6
5s
95
NO
2
NO2
NO
OCH
2
NO2
3
Reaction conditions: ArX (0.3 mmol), 2-methoxy-1-naphthylboronic acid (0.33 mmol), CsF (0.99 mmol), dioxane (2 mL), 100 ꢀC.
a
Isolated yields, based on ArX, average of two runs.
Coupling of heteroaryl bromides with 2-methoxy-1-
naphthylboronic acid in the described catalyst system were
also investigated. In case of 2-bromopyridine, the use of
0.1 mol% of catalyst gave a 33% isolated product yield
(entry 15). Comparing to 2-bromopyridine, 3-bromopyri-
dine gave a 78% yield (entry 16). In addition, 2-bromothi-
ophene and 3-bromothiophene were also studied with this
system. They gave 71% and 65% product yields respectively
(entries 17 and 18).
In contrast to corresponding aryl bromides, this catalyst
showed decreasing even no activity for the coupling of aryl
chlorides (entries 1, 5, 19, 20). The activated aryl chlorides

H. Li et al. / Journal of Organometallic Chemistry 691 (2006) 5688–5696
5693
such as 4-chloronitrobenzene, 3-chloronitrobenzene and 2,
4-dinirochlorobenzene, nevertheless, gave moderate to high
yield (entries 21–23).
solid. The resulting material was resuspended in CH2Cl2
(50 mL) with stirring for 0.5 h, filtered, and washed with
cold CH2Cl2 (20 mL), yielding 2-methoxy-1-naphthylbo-
ronic acid as a white solid. Yield: 13.4 g, 70%. M.p. 117–
In summary, we have demonstrated that simple triphe-
nylphosphine adduct of cyclopalladated ferrocenylimine 2
is an efficient catalyst for the synthesis of ortho-substituted
biaryls by the Suzuki cross-coupling between 2-methoxy-1-
naphthylboronic acid and aryl halides under atmospheric
conditions. Fourteen new ortho-substituted biaryls were
synthesized using this method. Applications of this class
of triphenylphosphine adducts in other palladium-cata-
lyzed reactions are currently under investigation in our
laboratory.
1
119 ꢀC. H NMR (400 MHz, CDCl3): d 4.03 (s, 3H), 6.11
(s, 2H), 7.28 (d, 1H, J = 9.0 Hz), 7.35–7.39 (m, 1H),
7.49–7.53 (m, 1H), 7.78 (d, 1H, J = 8.1Hz), 7.94 (d, 1H,
J = 9.0 Hz), 8.84 (d, 1H, J = 8.7 Hz).
3.3. General procedure for the coupling reactions
A 5 mL round-bottom flask was charged with aryl
halides (0.3 mmol), 2-methoxy-1-naphthylboronic acid
(67 mg, 0.33 mmol) and base (0.99 mmol). The catalyst
was introduced as a solvent solution (0.11 mg/mL) via syr-
inge, and additional solvent was added to give a total vol-
ume of 2 mL. The reaction mixture was stirred at reflux
until the starting aryl halides had been completely con-
sumed, as monitored by thin-layer chromatography. After
cooling to room temperature, water was added and the mix-
ture was extracted with dichloromethane. The combined
organic phases were dried with magnesium sulfate. The dry-
ing agent was filtered out and solvents were removed under
reduced pressure. The residue was purified by column chro-
matography on silica gel. Coupled products 5a [18], 5k [18],
5l [18], 5m [18] and 5p [19] exhibited spectral data and phys-
ical properties consistent to those reported in the literature.
Other new products were identified by Elemental analyses,
IR, NMR and mass spectra.
3. Experimental
3.1. General
Reactions were monitored by thin-layer chromatogra-
phy, which was carried out on silica gel coated glass plates
(60 F254). Melting points were measured with the use of a
WC-1 microscopic apparatus. Elemental analyses were
conducted with a Carlo Erba 1160 elemental analyzer. IR
spectra were collected on a Bruker VEC-TOR22 spectro-
1
photometer in KBr pellets. H and 13C NMR spectra were
recorded on a Bruker DPX-400 spectrometer in CDCl3
with TMS as an internal standard. Mass spectra were
recorded with the use of a LC-MSD-Trap-XCT mass spec-
trometer. High-resolution mass spectra were measured on a
Waters Q-Tof Microꢂ spectrometer. Preparative TLC was
performed on dry silica gel plates and developed with
selected appropriate solvents as eluent. 1,2-Dimethoxye-
thane (DME), toluene and dioxane were dried over Na/
benzophenone and distilled prior to usage. Cyclopalladated
ferrocenylimine 1 and 2 [15] and 1-bromo-2-methoxynaph-
thalene [16] were prepared according to previously reported
procedures. All aryl halides were purchased and used with-
out further treatment.
3.3.1. 2-Methoxy-1-phenylnaphthalene (5a) [18]
White solid, m.p. 50–51 ꢀC (lit. 70–72 ꢀC); 1H NMR
(400 MHz, CDCl3): d 3.83 (s, 3H), 7.32–7.34 (m, 2H),
7.35–7.38 (m, 3H), 7.40–7.44 (m, 1H), 7.48–7.52 (m, 3H),
7.81–7.83 (m, 1H), 7.88 (d, 1H, J = 9.2Hz) ppm; MS m/z
235.0 [M+H]+.
3.3.2. 2-Methoxy-1-(4-methylphenyl)-naphthalene (5b)
White solid, m.p. 99–101 ꢀC; Anal. Calc. for C18H16O:
C, 87.06; H, 6.49. Found: C, 86.95; H, 6.44%. IR: 2984,
2947, 1616, 1591, 1506, 1542, 1378, 1329, 1253, 1179,
1149, 1118, 1058, 1017, 897, 809, 742, 662, 563,
3.2. Preparation of 2-methoxy-1-naphthylboronic acid (4)
[3e,16,17]
1
A solution of 1-bromo-2-methoxynaphthalene (22.5 g,
0.095 mol) in THF (120 mL) was added dropwise to Mg
(2.7 g, 0.011 mol, activated by stirring for 24 h under argon
at room temperature). The reaction mixture was stirred at
room temperature for 2 h then at 50 ꢀC for 1 h, followed by
cooling to ꢀ78 ꢀC. Tributylborate (43.7 g, 0.190 mol) was
then added slowly, incubated at ꢀ78 ꢀC for 2 h. The mix-
ture was allowed to warm up to room temperature and stir-
red overnight. Water (25 mL) was added with stirring until
a homogeneous solution was reached. The mixture evapo-
rated in vacuum. The residue was acidified with HCl (1 M,
250 mL) until the purple color disappeared. The aqueous
solution was extracted with CH2Cl2 (3 · 50 mL), and the
organic layers were combined and dried over anhydrous
MgSO4, filtered, and concentrated, resulting in a brown
505 cmꢀ1; H NMR (400 MHz, CDCl3): d 2.45 (s, 3H),
3.84 (s, 3H), 7.24–7.27 (m, 2H), 7.30–7.34 (m, 4H), 7.36
(d, 1H, J = 9.0 Hz), 7.50–7.53 (m, 1H), 7.80–7.83 (m,
1H), 7.87 (d, 1H, J = 9.0 Hz) ppm; 13C NMR(100 MHz,
CDCl3): d 21.4 (CH3), 56.8 (CH3), 113.8 (CH), 123.5
(CH), 125.4 (CH), 126.2 (CH), 127.9 (CH), 128.9 (C),
128.9 (CH), 129.0(double CH), 129.1 (C), 130.8(double
CH), 133.3 (C), 133.8 (C), 136.7 (C), 153.8 (C) ppm; MS
m/z 249.0 [M+H]+.
3.3.3. 2-Methoxy-1-(4-methoxyphenyl)-naphthalene (5c)
White solid, m.p. 129–131 ꢀC; Anal. Calc. for C18H16O2:
C, 81.79; H, 6.10. Found: C, 81.82; H, 6.08%. IR: 3004,
2936, 2837, 1610, 1510, 1460, 1378, 1330, 1247, 1176,
1
1149, 1121, 1064, 1028, 832, 813, 745, 564, 528 cmꢀ1; H

5694
H. Li et al. / Journal of Organometallic Chemistry 691 (2006) 5688–5696
NMR (400 MHz, CDCl3): d 3.84 (s, 3H), 3.89 (s, 3H),
7.03–7.06 (m, 2H), 7.28–7.29 (m, 2H), 7.30–7.32 (m, 2H),
7.36 (d, 1H, J = 8.8 Hz), 7.53–7.55 (m, 1H), 7.80–7.83
(m, 1H), 7.87 (d, 1H, J = 9.2Hz) ppm; 13C NMR
(100 MHz, CDCl3): d 55.3 (CH3), 56.8 (CH3), 113.7(double
CH), 113.8 (CH), 123.5 (CH), 125.0 (C), 125.3 (CH), 126.2
(CH), 127.8 (CH), 128.4 (C), 128.9 (CH), 129.0 (C),
132.0(double CH), 133.9 (C), 153.9 (C), 158.6 (C) ppm;
MS m/z 265.0 [M+H]+.
1254, 1150, 1065, 857, 816, 752, 702 cmꢀ1 1H NMR
;
(400 MHz, CDCl3): d 3.84 (s, 3H), 7.34–7.38 (m, 4H),
7.52–7.55 (m, 2H), 7.83–7.85 (m, 1H), 7.93 (d, 1H,
J = 9.1 Hz), 8.32–8.34 (m, 2H) ppm; 13C NMR(100 MHz,
CDCl3): d 56.5 (CH3), 113.2 (CH), 122.5 (C), 123.4(double
CH), 123.8 (CH), 124.3 (CH), 127.0 (CH), 128.2 (CH),
128.9 (C), 130.4 (CH), 132.2(double CH), 132.7 (C), 144.0
(C), 147.0 (C), 153.6 (C) ppm; MS m/z 280.0 [M+H]+.
3.3.8. 4-(2-Methoxy-1-naphthalene)-benzonitrile (5h)
White solid, m.p. 129–130 ꢀC; Anal. Calc. for
C18H13NO: C, 83.37; H, 5.05, N, 5.40. Found: C, 83.30;
H, 4.92; N, 5.18%. IR: 2984, 2228, 1599, 1506, 1468,
1434, 1384, 1333, 1256, 1064, 1019, 905, 840, 821, 749,
3.3.4. 2-Methoxy-1-[4-(N,N-dimethylamino)phenyl]-
naphthalene (5d)
White solid, m.p. 158–160 ꢀC; Anal. Calc. for
C19H19NO: C, 82.28; H, 6.90; N, 5.05. Found: C, 82.18;
H, 6.82; N, 4.85%. IR: 2936, 1612, 1524, 1459, 1381,
1
552 cmꢀ1; H NMR (400 MHz, CDCl3): d 3.82 (s, 3H),
1357, 1256, 1227, 1064, 810, 754 cmꢀ1
;
1H NMR
7.33–7.36 (m, 4H), 7.45–7.47 (m, 2H), 7.73–7.75 (m, 2H),
7.81–7.84 (m, 1H), 7.91 (d, 1H, J = 9.2 Hz) ppm; 13C
NMR (100 MHz, CDCl3): d 56.4 (CH3), 110.7 (C), 113.1
(CH), 119.1 (C), 122.8 (C), 123.7 (CH), 124.2 (CH), 126.8
(CH), 128.0 (CH), 128.8 (C), 130.1 (CH), 131.8(double
CH), 131.9(double CH), 132.7 (C), 141.7 (C), 153.4 (C)
ppm; MS m/z 260.0 [M+H]+.
(400 MHz, CDCl3): d 3.03 (s, 6H), 3.83 (s, 3H), 6.89 (d,
2H, J = 8.1 Hz), 7.25–7.28 (m, 2H), 7.29–7.34 (m, 2H),
7.35 (d, 1H, J = 9.1 Hz), 7.61–7.64 (m, 1H), 7.78–7.81
(m, 1H), 7.83 (d, 1H, J = 9.0 Hz) ppm; 13C MR
(100 MHz, CDCl3): d 40.7 (CH3), 56.9 (CH3), 112.3 (C),
114.0 (CH), 123.4 (CH), 124.0 (C), 125.6 (CH), 126.0
(CH), 127.8 (CH), 128.4 (CH), 129.2 (C), 131.7(double
CH), 134.1 (C), 149.4 (C), 154.0 (C) ppm; MS m/z 277.9
[M+H]+.
3.3.9. 2-Methoxy-1-(4-Trifluoroacetphenyl)-naphthalene
(5i)
White solid, m.p. 99–100 ꢀC; Anal. Calc. for
C18H13F3O: C, 71.52; H, 4.33. Found: C, 71.45; H,
4.18%. IR: 2969, 2844, 1620, 1592, 1507, 1466, 1327,
3.3.5. 4-(2-Methoxy-1-Naphthalene)-phenylethanone (5e)
White solid, m.p.145–147 ꢀC; Anal. Calc. for C19H16O2:
C, 82.58; H, 5.84. Found: C, 82.57; H, 5.65%. IR: 2936,
1679, 1599, 1506, 1461, 1402, 1356, 1332, 1268, 1061,
1255, 1163, 1121, 1066, 1019, 834, 809, 749 cmꢀ1 1H
;
NMR (400 MHz, CDCl3): d 3.83 (s, 3H), 7.32–7.37 (m,
3H), 7.39–7.42 (m, 1H), 7.48 (d, 2H, J = 8.0 Hz), 7.74 (d,
2H, J = 8.1 Hz), 7.81–7.85 (m, 1H), 7.90 (d, 1H,
J = 9.1 Hz) ppm; 13C NMR(100 MHz, CDCl3): d 56.6
(CH3), 113.5 (CH), 123.6 (C), 123.7 (CH), 124.5(q,
J = 270 Hz, CF3), 124.7 (CH), 125.1(q, J = 3.6 Hz, double
CH), 126.7 (CH), 128.0 (CH), 129.0 (C), 129.2(q,
J = 32.2Hz, C), 129.8 (CH), 131.5 (double CH), 133.2
(C), 140.5 (C), 153.7 (C) ppm; MS m/z 325.1 [M+Na]+.
1017, 843, 817, 760, 614 cmꢀ1 1H NMR (400 MHz,
;
CDCl3): d 2.68 (s, 3H), 3.84 (s, 3H), 7.33–7.39 (m, 3H),
7.41–7.45 (m, 1H), 7.47–7.50 (m, 2H), 7.82–7.85 (m, 1H),
7.91 (d, 1H, J = 9.1Hz), 8.08–8.11 (m, 2H) ppm; 13C
NMR(100 MHz, CDCl3): d 26.7 (CH3), 56.6 (CH3), 113.4
(CH), 123.7 (CH), 123.9 (C), 124.7 (CH), 126.7 (CH),
128.0 (CH), 128.2(double CH), 128.9 (C), 129.7 (CH),
131.4(double CH), 133.0 (C), 135.8 (C), 142.0 (C), 153.6
(C), 198.0 (C@O) ppm; MS m/z 277.0 [M+H]+.
3.3.10. 3-(2-Methoxy-1-naphthalene)-benzaldehyde (5j)
White solid, m.p. 89–91 ꢀC; Anal. Calc. for C18H14O2:
C, 82.42; H, 5.38. Found: C, 82.18; H, 5.15%. IR: 3050,
3001, 2936, 2837, 1689, 1620, 1594, 1508, 1465, 1374,
1331, 1256, 1176, 1148, 1113, 1062, 1018, 916, 810, 747,
3.3.6. 2-Methoxy-1-(4-Chlorophenyl)-naphthalene (5f)
White solid, m.p. 81 ꢀC; Anal. Calc. for C17H13ClO: C,
75.98; H, 4.88. Found: C, 76.08; H, 4.72%. IR: 2963, 1620,
1592, 1494, 1464, 1381, 1331, 1255, 1067, 1017, 807, 750,
1
506 cmꢀ1
;
1H NMR (400 MHz, CDCl3): 3.82 (s, 3H),
695, 646, 600 cmꢀ1; H NMR (400 MHz, CDCl3): d 3.83
7.28–7.31 (m, 2H), 7.32–7.35 (m, 3H), 7.44–7.47 (m, 3H),
7.80–7.82 (m, 1H), 7.87 (d, 1H, J = 8.8 Hz) ppm; 13C
NMR(100 MHz, CDCl3): d 56.7 (CH3), 113.6 (CH),
123.7 (CH), 123.9 (C), 125.0 (CH), 126.6 (CH), 128.0
(CH), 128.5(double CH), 129.0 (C), 129.5 (CH), 132.5(dou-
ble CH), 133.1 (C), 133.4 (C), 134.9 (C), 153.8 (C) ppm; MS
m/z 269.6 [M+H]+.
(s, 3H), 7.33–7.42 (m, 4H), 7.64–7.65 (m, 2H), 7.82–7.84
(m, 1H), 7.89–7.95 (m, 3H), 10.07 (s, 1H) ppm; 13C
NMR (100 MHz, CDCl3): d 56.6 (CH3), 113.5 (CH),
123.5 (C), 123.7 (CH), 124.7 (CH), 126.8 (CH), 128.1(dou-
ble CH), 129.0 (CH), 129.1 (C), 129.8 (CH), 133.0 (CH),
133.3 (C), 136.6 (C), 137.4 (CH), 137.6 (C), 153.8 (C),
192.5 (C@O) ppm; MS m/z 262.9 [M+H]+.
3.3.7. 2-Methoxy-1-(4-nitrophenyl)-naphthalene (5g)
Light yellow solid, m.p. 109–111 ꢀC; Anal. Calc. for
C17H13NO3: C, 73.11; H, 4.69; N, 5.02. Found: C, 73.00;
H, 4.57; N, 4.80%. IR: 2934, 1594, 1515, 1459, 1346,
3.3.11. 2-Methoxy-1-(2-methylphenyl)-naphthalene (5k)
[18]
White solid, m.p. 92–94 ꢀC (lit. 95–96 ꢀC); 1H NMR
(400 MHz, CDCl3): d 1.99 (s, 3H), 3.82 (s, 3H), 7.18 (d,

H. Li et al. / Journal of Organometallic Chemistry 691 (2006) 5688–5696
5695
1
1H, J = 6.8 Hz), 7.24–7.37 (m, 7H), 7.81–7.83 (m, 1H),
7.88 (d, 1H, J = 9.0 Hz) ppm; MS m/z 249.1 [M+H]+.
654 cmꢀ1; H NMR (400 MHz, CDCl3): d 3.94 (s, 3H),
7.29–7.31 (m, 1H), 7.42–7.50 (m, 4H), 7.54–7.56 (m, 1H),
7.82(d, 1H, J = 8.4 Hz), 7.91 (d, 1H, J = 7.5 Hz), 7.95(d,
1H, J = 9.0 Hz) ppm; 13C NMR (100 MHz, CDCl3): d
56.8 (CH3), 113.9 (CH), 120.3 (C), 123.7 (CH), 124.6
(CH), 124.7 (CH), 125.3 (CH), 126.6 (CH), 128.0 (CH),
129.2 (C), 129.3 (CH), 130.6 (CH), 134.0 (C), 135.9 (C),
154.4 (C) ppm; HRMS (positive ESI) Calc. for
C15H12OS: 241.0687 [M+H]+, Found: 241.0682 [M+H]+.
3.3.12. 2-Methoxy-1-(2,6-dimethylphenyl)-naphthalene (5l)
[18]
White solid, m.p. 95–97 ꢀC (lit. 96–98 ꢀC); 1H NMR
(400 MHz, CDCl3): d 1.88 (s, 6H), 3.84 (s, 3H), 7.14 (d,
1H, J = 8.8 Hz), 7.18 (d, 2H, J = 7.3Hz), 7.24 (d, 1H,
J = 5.9 Hz), 7.27–7.34 (m, 2H), 7.38 (d, 1H, J = 8.8 Hz),
7.83 (d, 1H, J = 7.3Hz), 7.89 (d, 1H, J = 9.1Hz) ppm;
MS m/z 262.9 [M+H]+.
3.3.18. 2-Methoxy-1-(3-nitrophenyl)-naphthalene (5r)
Light yellow solid, m.p.103–104 ꢀC; Anal. Calc. for
C17H13NO3: C, 73.11; H, 4.69; N, 5.02. Found: C, 73.00;
H, 4.47; N, 4.71%. IR: 2939, 1616, 1591, 1527, 1467,
3.3.13. 2-Methoxy-1,10-binaphthyl (5m) [18]
White solid, m.p. 106–107 ꢀC (lit. 106–107 ꢀC); 1H
NMR (400 MHz, CDCl3): d 3.74 (s, 3H), 7.14 (d, 1H,
J = 8.7 Hz), 7.19–7.33 (m, 4H), 7.42–7.46 (m, 3H), 7.58–
7.62 (m, 1H), 7.85 (d, 1H, J = 8.0 Hz), 7.91–7.98 (m, 3H)
ppm; MS m/z 284.1 [M+H]+.
1351, 1260, 1066, 1121, 1066, 812, 748, 686 cmꢀ1 1H
;
NMR (400 MHz, CDCl3): d 3.84 (s, 3H), 7.34–7.40 (m,
4H), 7.62–7.66 (m, 1H), 7.69–7.72 (m, 1H), 7.83–7.86 (m,
1H), 7.93 (d, 1H, J = 9.0 Hz), 8.26–8.29 (m, 2H) ppm;
13C NMR (100 MHz, CDCl3): d 56.4 (CH3), 113.1 (CH),
122.1 (CH), 122.2 (C), 123.8 (CH), 124.2 (CH), 126.2
(CH), 127.0 (CH), 128.1 (CH), 128.9 (C), 129.0 (CH),
130.2 (CH), 132.9 (C), 137.5 (CH), 138.2 (C), 148.3 (C),
153.7 (C) ppm; MS m/z 280.0 [M+H]+.
3.3.14. 2-(2-Methoxy-1-naphthalene)-pyridine (5n)
Colorless oil; IR: 3054, 2969, 2844, 1622, 1591, 1509,
1464, 1337, 1257, 1149, 1069, 1021, 811, 749 cmꢀ1 1H
;
NMR (400 MHz, CDCl3): d 3.83 (s, 3H), 7.30–7.36 (m,
4H), 7.40–7.45 (m, 2H), 7.78–7.82 (m, 2H), 7.90 (d, 1H,
J = 9.1 Hz), 8.81(d, 1H, J = 4.7 Hz) ppm; 13C NMR
(100 MHz, CDCl3): d 56.8 (CH3), 113.6 (CH), 122.0
(CH), 123.7 (CH), 124.0 (C), 124.7 (CH), 126.7 (CH),
126.8 (CH), 128.0 (CH), 129.1 (C), 130.2 (CH), 133.3 (C),
136.2 (CH), 149.6 (CH), 154.2 (C), 156.3 (C) ppm; HRMS
(positive ESI) Calc. for C16H13NO: 236.1075 [M+H]+,
Found: 236.1075 [M+H]+.
3.3.19. 2-Methoxy-1-(2,4-dinitrophenyl)-naphthalene (5s)
Yellow solid, m.p.225–227 ꢀC; Anal. Calc. for
C17H12N2O5: C, 62.96; H, 3.73; N, 8.64. Found: C, 62.79;
H, 3.65; N, 8.59%. IR: 2943, 1604, 1526, 1346, 1263,
1064, 904, 820, 749, 713 cmꢀ1 1H NMR (400 MHz,
;
CDCl3): d 3.81 (s, 3H), 7.31–7.34 (m, 2H), 7.38–7.43 (m,
2H), 7.67 (d, 1H, J = 8.4Hz), 7.86–7.89 (m, 1H), 7.98 (d,
1H, J = 9.1Hz), 8.54 (d, 1H, J = 8.5 Hz), 8.95 (s, 1H)
ppm; 13C NMR (100 MHz, CDCl3): d 56.1 (CH3), 112.4
(CH), 118.0 (C), 120.0 (CH), 123.3 (CH), 124.1 (CH),
126.6 (CH), 127.6 (CH), 128.5 (CH), 129.0 (C), 131.3
(CH), 131.9 (C), 135.2 (CH), 138.3 (C), 147.1 (C), 150.4
(C), 153.1 (C) ppm; MS m/z 325.0 [M+H]+.
3.3.15. 3-(2-Methoxy-1-naphthalene)-pyridine (5o)
White solid, m.p. 124 ꢀC; Anal. Calc. for C16H13NO: C,
81.68; H, 5.57; N, 5.95. Found: C, 81.44; H, 5.46; N,
5.72%. IR: 2999, 2929, 1620, 1590, 1507, 1462, 1380, 1332,
1261, 1142, 1073, 1024, 808, 747, 714 cmꢀ1 1H NMR
;
(400 MHz, CDCl3): d 3.84 (s, 3H), 7.35–7.39 (m, 3H),
7.43–7.46 (m, 2H), 7.73 (d, 1H, J = 7.6 Hz), 7.83–7.85 (m,
1H), 7.93 (d, 1H, J = 9.0 Hz), 8.65(d, 1H, J = 9.0 Hz),
8.67 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3): d 56.5
(CH3), 113.3 (CH), 121.1 (C), 123.0 (CH), 123.8 (CH),
124.5 (CH), 126.8 (CH), 128.1 (CH), 129.0 (C), 130.1
(CH), 132.3 (C), 133.3 (C), 138.8 (CH), 148.1 (CH), 151.7
(CH), 154.1 (C) ppm; MS m/z 235.9 [M+H]+.
Acknowledgements
We are grateful to the National Natural Science Foun-
dation of China (Project 20472074) and the Innovation
Found for Outstanding Scholar of Henan Province (Pro-
ject 0621001100) for the financial support given to this re-
search. We thank professor Zhu Zhiwu for valuable
discussion of this paper.
3.3.16. 2-(2-Methoxy-1-naphthalene)-thiophene (5p) [19]
1
Colorless oil; H NMR (400 MHz, CDCl3): d 3.87 (s,
3H), 7.08 (d, 1H, J = 3.3Hz), 7.18–7.20 (m, 1H), 7.30–
7.35 (m, 2H), 7.36–7.40 (m, 1H), 7.48 (d, 1H, J =
5.4 Hz), 7.73 (d, 1H, J = 8.4 Hz), 7.79 (d, 1H, J =
8.8 Hz), 7.87 (d, 1H, J = 9.0 Hz) ppm; MS m/z 240.9
[M+H]+.
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