Double-coupling of dibromo arenes with aryltriolborates for synthesis of diaryl-substituted planar frameworks

Article abstract of DOI:10.1016/j.tet.2011.06.083

A new method for simple and practical synthesis of diaryl-substituted arenes using potassium aryltriolborates was developed. Double-cross-coupling of dibromo arenes with aryltriolborates was carried out in the presence of a palladium catalyst, such as Pd(

Full text of DOI:10.1016/j.tet.2011.06.083

Tetrahedron 67 (2011) 6804e6811
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Double-coupling of dibromo arenes with aryltriolborates for synthesis
of diaryl-substituted planar frameworks
*
Gao-Qiang Li, Yasunori Yamamoto , Norio Miyaura
Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 20 May 2011
Received in revised form 24 June 2011
Accepted 24 June 2011
Available online 6 July 2011
A new method for simple and practical synthesis of diaryl-substituted arenes using potassium aryl-
triolborates was developed. Double-cross-coupling of dibromo arenes with aryltriolborates was carried
out in the presence of a palladium catalyst, such as Pd(OAc)2, Pd(PPh3)4 or Pd(OAc)2/BIPHEP. The use of
CuCl (40 mol %) with a palladium catalyst was found to be highly effective to give diaryl-substituted
aromatic compounds in good yields.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Aryltriolborates
Palladium catalyst
Cross-coupling reaction
Dibromo arenes
Double arylation
1. Introduction
advantage of the difficult or impossible rotations of aryl rings along
the naphthalene axis. For example, 1,8-diacridyl-, 1,8-diquinolyl-,
Over the past 3 decades, it has become increasingly clear that
organoboronic acids are valuable reagents capable of undergoing
many catalytic CeC bond formations in organic synthesis.1 Much
interest has recently been shown in hindered cross-coupling re-
actions due to the presence of ortho-substituted biaryls in natural
products, biologically active compounds, and valuable materials.2
On the other hand, there has been a large number of reports of se-
lective couplings with di- or trihalo aromatic compounds, because of
the steric hindrance of second and third couplings.3ꢀ8 Diiodo arenes
were the best choice for the double couplings, and dibromo arenes
mainly yielded single coupling products.5 In addition, although
many excellent ligands have been developed for different sub-
strates,5 these procedures suffer from lack of generality.
and 1,8-dipyridyl-naphthalenes have been developed for new
photoluminescent or chiral sensors.11 Results of some studies on
diaryl biphenylene have also been.14 However, the incorporation of
bulky aryl rings into the peri position of naphthalene, biphenylene,
and their analogues is still synthetically challenging due to severe
steric hindrance to carbonecarbon bond formation and often un-
successful reactions or reactions resulting in low yields.6e8,14,15
We recently reported that aryltriolborates, which have good
stability in air- and water, undergo very smooth and fast trans-
metalation to various transition metal complexes. The utility of these
tetra-coordinated arylboron compounds has already been demon-
strated in palladium-catalyzed cross-coupling,22,23 copper-catalyzed
N-arylation of amines24 and rhodium-catalyzed 1,4-addition to
enones.25 For the synthesis of biaryls, we have used DMF and water
as a solvent, 3 mol % Pd(OAc)2 as a catalyst, without a ligand and base,
to give biaryls in very high yields.22a Herein, we report the utilization
of aryltriolborates to provide efficient and facile synthesis of highly
congested diaryl-substituted planar frameworks (Scheme 1).
Diaryl-substituted planar frameworks, such as naphthalene,9e13
biphenylene,14,15 dibenzothiophene,16 dibenzofuran,15 and xan-
thene15,17 have fascinating scaffolds with unusual geometry in or-
ganic molecules. The two aryl units bonded to planar frameworks
in sufficiently close positions provide a parallel face-to-face ar-
rangement, thus indicating
pep interactions that play an impor-
tant role in a variety of chemical properties, such as molecular
recognition,18 stereocontrolled reactions,19 protein and nucleic acid
structures,20 and crystal packing.21 Some applications have taken
2. Results and discussion
Most of the Pd-catalyzed reactions described for the synthesis of
diaryl-substituted planar frameworks involved the use of a phos-
phine ligand and base, with a strong base being used to obtain
satisfactory yields, which sometimes caused serious problems, such
as functional group compatibility and contamination. In our
* Corresponding author. Tel./fax: þ81 11 706 6560; e-mail address: yasuyama@
eng.hokudai.ac.jp (Y. Yamamoto).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.06.083

G.-Q. Li et al. / Tetrahedron 67 (2011) 6804e6811
6805
previous work, when aryltriolborates were used for palladium-
catalyzed cross-coupling reactions,22 the use of a phosphine li-
gand and base could sometimes be avoided.
Ar1
Ar1
Br
Br
K+
O
[Pd]
To further show the efficiency of this methodology, we first tried
to synthesize ortho-disubstituted benzene, pyridine, thiophene,
and furan (Table 1, entries 1e6). ortho-Disubstituted benzene was
obtained in excellent yields, 92% yield being obtained even for
highly congested di(2-naphthyl)substituted benzene. However,
only moderate yield (60%) was observed for ortho-disubstituted
heteroaromatics, such as ortho-diaryl-substituted pyridine. To
compensate this deficiency, we tried another reaction system de-
scribed for the synthesis of tetra-ortho-substituted biaryls,22d
which could avoid the use of a base and greatly improve the
functional group tolerance. As expected, ortho-disubstituted pyri-
dine, thiophene, and furan were obtained in high yields (Table 1,
entries 4e6). The yield of ortho-diaryl-substituted pyridine was
greatly improved from 60 to 91% (Table 1, entries 3 and 4).
Next, we designed five kinds of aryl dibromides (2eei) with
different distances and angles between two carbonebromide
bonds, and then we used 4-tolyltriolborate (1b) to synthesize
diaryl-substituted planar frameworks according to the procedure
described in our previous report.22a When 2.4 equiv of aryl-
triolborate (1b) was used, diaryl arenes (3beei) were obtained in
excellent yields without the use of a ligand and base at room
temperature (Table 1, entries 7e11).
B-
+
Ar2
Ar2
O
O
Ar1
1
2
3
K+
K+
Br
Br
Br
Br
O
Br
Br
O
S
B-
B-
O
O
O
O
O
O
O
O
2a
2f
1e
1a
Br
O
K+
K+
K+
N
Br
Br
O
K+
B-
O
2b
O
O
B-
2g
S
Br
Br
Br
Br
Br
1b
2c
1f
O
B-
O
2h
Br
K+
O
2d
B-
Br
Ph2N
O
O
O
1c
Br Br
O
t
t
Bu
Bu
B-
O
O
2i
2e
1g
1d
Ph2N
Scheme 1. Double-coupling of dibromo arenes with potassium aryltriolborates.
We next synthesized biphenyltriolborate (1c) to prepare dif-
ferent diaryl-substituted frameworks. Compounds 3ce and 3cf
Table 1
Double-cross-coupling of dibromo arenes with aryltriolborates
Entry 1 (Ar1])
2
Conditions
3
Yield (%) Entry 1 (Ar1])
2
Conditions
B
3
Yield (%)
Br
Br
Br
Br
Br
Br
S
1
2
3
4
2-Naphthyl (1a)
Aa
3aa 92
3ba 86
3bb 60
3bb 91
17
18
19
20
4-Ph2NC6H4 (1d)
4-Ph2NC6H4 (1d)
4-Ph2NC6H4 (1d)
4-Ph2NC6H4 (1d)
3df 84
3dg 79
3dh 82
3di 80
2a
2a
2b
2b
2f
Br
Br
O
4-Tolyl (1b)b
4-Tolyl (1b)b
4-Tolyl (1b)
Aa
Aa
B
B
B
B
2g
Br
Br
Br
Br
Br
N
N
2h
Br
Br
Br
O
t
t
Bu
Bu
2i
Br Br
Br
Br
5
4-Tolyl (1b)c
B
3bc 87
21
4-PhC^CC6H4 (1e)
C
3ee 76
S
2c
2e
Br
Br
Br
Br
Br
S
6
7
8
4-Tolyl (1b)
4-Tolyl (1b)d
4-Tolyl (1b)d
B
A
A
3bd 81
3be 86
3bf 90
22
23
24
4-PhC^CC6H4 (1e)
4-PhC^CC6H4 (1e)
4-PhC^CC6H4 (1e)
C
3ef 88
3eg 90
3ei 97
O
2d
2f
Br Br
Br
O
C
2g
2e
Br
Br
Br
Br
O
S
Ce
t
t
Bu
Bu
(continued on next page)
2f
2i

6806
G.-Q. Li et al. / Tetrahedron 67 (2011) 6804e6811
Table 1 (continued )
Entry 1 (Ar1])
2
Conditions
A
3
Yield (%) Entry 1 (Ar1])
2
Conditions
C
3
Yield (%)
Br
Br Br
Br
O
Ph2N
9
4-Tolyl (1b)d
4-Tolyl (1b)d
4-Tolyl (1b)d
3bg 83
3bh 91
3bi 98
25
26
27
3fe 82
3ff 83
3fg 54
3fg 74
(1f)
(1f)
(1f)
2g
2e
Br
Br
Br
Br
Br
Br
Br
S
O
O
Ph2N
Ph2N
10
11
A
A
C
B
2f
2h
Br
Br
Br
O
t
t
Bu
Bu
2g
2i
Br Br
Ph2N
Ph2N
12
13
14
15
4-Biphenyl (1c)
4-Biphenyl (1c)
4-Biphenyl (1c)
4-Biphenyl (1c)
A
A
B
B
3ce 87
3cf 98
3cg 84
3ci 90
28
29
30
31
C
C
C
C
(1f)
(1f)
2g
2e
Br
Br
Br
Br
Br
O
S
3fi
90
t
t
Bu
Bu
2f
2i
Br Br
Br
O
3ge 81
3gh 71
2g
(1g)
(1g)
2e
Br
Br
Br
Br
Br
O
t
t
Bu
Bu
2h
2i
Br
Br Br
O
16
4-Ph2NC6H4 (1d)
B
3de 88
32
C
3gi 89
t
t
Bu
Bu
2e
(1g)
2i
Condition A: triolborate (1, 3.0 equiv), Pd(OAc)2 (10 mol %), DMF/H2O (4/1, 10 mL), rt, 16 h.
Condition B: triolborate (1, 3.0 equiv), Pd(OAc)2 (10 mol %)/BIPHEP (2,20-bis(diphenylphosphino)biphenyl, 11 mol %), CuCl (0.4 equiv), DMF (15 mL), 80 ꢁC, 14 h.
Condition C: triolborate (1, 3.0 equiv), Pd(PPh3)4 (10 mol %), K2CO3 (2 equiv), DMF (15 mL), 80 ꢁC, 14 h.
a
Pd(OAc)2 (6 mol %) was used.
Triolborate (1, 2.2 equiv) was used.
Triolborate (1, 4.0 equiv) was used.
Triolborate (1, 2.4 equiv) was used.
b
c
d
e
Toluene was used.
were obtained successfully in 87% and 98% yields, respectively, by
the same procedure with 3 equiv of biphenyl triolborate (1c) (Table
1, entries 12 and 13). Unfortunately, when biphenyl triolborate (1c)
was used for reaction with dibromides 2g and 2i, no desired
products were obtained. In our previous work, we found that
aryltriolborate could be used for hindered coupling by using
Pd(OAc)2 and CuCl as co-catalysts, and BIPHEP (2,20-bis(diphenyl-
phosphino)biphenyl) as a ligand without the use of a base to syn-
thesize tetra-ortho-substituted biaryls in high yields.22d When this
method was used, 3cg and 3ci were obtained smoothly in 84% and
90% yields, respectively (Table 1, entries 14 and 15).
To further show the advantage of aryltriolborates, we compared
the reactivities of boronic acid and aryltriolborate (1d) in the cou-
pling reaction of congested 1,8-dibromonaphthalene. As shown in
Table 2, when 3 equiv of boronic acid was used to furnish the
coupling with 1,8-dibromonaphtalene, the Pd(OAc)2/CuCl system
did not give the desired product; when 10 mol % Pd(PPh3)4 and
2 equiv of K2CO3 were used, 33% isolated yield was achieved.
However, without the use of a base, no desired product was
obtained. In contrast, when 3 equiv of aryltriolborates was used for
the coupling, the Pd(OAc)2/CuCl system gave 88% yield (entry 6);
without a base, when 10 mol % Pd(PPh3)4 was used, 77% isolated
yield was also observed (entry 4), and when 2 equiv of K2CO3 was
used, the yield was slightly improved to 84% (entry 5). From the
results, we conclude that aryltriolborates undergo very fast and
smooth transmetalation compared with boronic acids.
Next, we synthesized aryltriolborates (1deg) used for electronic
materials. We used triolborate (1d) to synthesize planar frame-
works by the Pd(OAc)2/CuCl system. Bis(4-(diphenylamino)phenyl)
arenes (3deei) were obtained in 88%, 84%, 79%, 82%, and 80% yields,
respectively (Table 1, entries 16e20).
When 4-(phenylethynyl)phenyltriolborate (1e) was used to
synthesize diaryl-substituted arenes, neither the Pd(OAc)2/DMF/
H2O reaction system nor the Pd(OAc)2/CuCl reaction system gave
the desired product. The reasons for this are not known. To achieve
coupling, we next tried using a Pd(PPh3)4/K2CO3 reaction system

G.-Q. Li et al. / Tetrahedron 67 (2011) 6804e6811
6807
7.51e7.58 (m, 2H), 7.68e7.70 (m, 2H), 7.81 (s,1H); 13C NMR (100 MHz,
DMSO-d6):
¼16.9, 35.2, 73.5, 124.2, 124.7, 124.8, 127.6, 128.1, 131.2,
Table 2
Reaction conditions for synthesis of 1,8-bis[4-(diphenylamino)phenyl] naphthalene
d
(3de)a
132.3, 132.5, 133.4 (CeB is not observed); 11B NMR (128 MHz, DMSO-
B(OH)2
d6):
d
¼4.80; MS (m/z): 122 (8),152 (10), 255 (Mꢀ,100); HRMS (FABꢀ):
NPh2
NPh2
Br
Br
Pd cat.
m/z calcd for C15H16BO3ꢀ: 255.1198; found: 255.1193.
+
or
B(OCH2)3CCH3K
Ph2N
DMF, 80°C
14 h
4.1.2. Potassium 4-tolyltriolborate (1b)22a. The synthesis of potas-
sium 4-tolyltriolborate 1b (96%) using 4-tolyl boronic acid was the
same as the synthesis of 2-naphthyl triolborate. 1H NMR (400 MHz,
Ph2N
1d
2e
3de
Entry
1
[Pd]
Ligand
Additive
(equiv)
Yieldb
(%)
DMSO-d6):
d
¼0.46 (s, 3H), 2.16 (s, 3H), 3.55 (s, 6H), 6.79 (d, J¼7.3 Hz,
2H), 7.18 (d, J¼7.3 Hz, 2H); 13C NMR (100 MHz, DMSO-d6):
¼16.5,
d
21.2, 34.6, 73.8, 126.5, 132.2, 132.3 (CeB is not observed); 11B NMR
(128 MHz, DMSO-d6):
d
¼4.62; HRMS (FABꢀ): m/z calcd for
1
Pd(PPh3)4 None
Pd(PPh3)4 None
None
Trace
Ph2N
B(OH)2
C17H18BO3ꢀ: 219.1198; found: 219.1197.
2
3
K2CO3 (2.0) 33
4.1.3. Potassium biphenyl triolborate (1c). The synthesis of potas-
sium biphenyl triolborate 1c (89%) using biphenyl boronic acid27 was
the same as the synthesis of 2-naphthyl triolborate. 1H NMR
Pd(OAc)2 BIPHEPc CuCl (0.4)
Trace
4
Pd(PPh3)4 None
Pd(PPh3)4 None
None
77
Ph2N
B(OCH2)3CCH3K
(400 MHz, DMSO-d6):
(m, 3H), 7.37e7.41 (m, 4H), 7.57e7.59 (m, 2H); 13C NMR (100 MHz,
DMSO-d6):
¼16.3, 34.5, 73.6, 123.9, 126.2, 126.2, 128.7, 132.8, 135.7,
d¼0.48 (s, 3H, CCH3), 3.59 (s, 6H), 7.25e7.30
d
5
6
K2CO3 (2.0) 84
88
141.7 (CeB is not observed); 11B NMR (128 MHz, DMSO-d6):
d
¼1.92;
Pd(OAc)2 BIPHEPc CuCl (0.4)
MS(m/z):122(9),153(42),199(11), 281(Mꢀ,100); HRMS (FABꢀ):m/z
calcd for C17H18BO3ꢀ: 281.1354; found: 281.1350; elemental analysis:
calcd (%) for C17H18BKO3: C, 63.76; H, 5.67; found: C, 62.75; H, 5.62.
a
A mixture of 1,8-dibromonaphthalene (2e, 0.2 mmol), 4-(diphenylamino)phe-
nyl boronic acid (3 equiv) or 4-(diphenylamino)phenyl triolborate (3 equiv) was
stirred at 80 ꢁC for 14 h in the presence of Pd catalyst (10 mol %).
b
Isolated yields.
BIPHEP (11 mol %) was used.
c
4.1.4. Potassium 4-(diphenylamino)phenyltriolborate (1d). The syn-
thesis of potassium 4-(diphenylamino)phenyl triolborate (1d)
(89%) using 4-(diphenylamino)phenylboronic acid28 was the same
as the synthesis of 2-naphthyl triolborate. 1H NMR (400 MHz,
(Table 2, entry 5). The corresponding diaryl arenes (3ee, 3ef, 3eg,
and 3ei) were isolated in 76%, 88%, 90%, and 97% yields, respectively
(Table 1, entries 21e24). This reaction system was also used for
4-((4-(diphenylamino)phenyl)ethynyl)phenyltriolborate (1f) and
pyrenyltriolborate (1g). Under condition B, the reaction of 1f with
2g gave the desired product in moderate yield (54%, Table 1, entry
27). Using condition C, however, the desired products (3fe, 3ff, 3fg,
and 3fi) were obtained in 82%, 83%, 74%, and 90% yields, re-
spectively (Table 1, entries 25, 26, 28, and 29). Similarly bis(pyrenyl)
arenes (3ge, 3gh, and 3gi) were obtained in 81%, 71%, and 89%
yields, respectively (Table 1, entries 30e32).
DMSO-d6):
d
¼0.45 (s, 3H), 3.55 (s, 6H), 6.71 (d, J¼8.0 Hz, 2H), 6.87
(t, J¼8.0 Hz, 6H), 7.17 (t, J¼8.0 Hz, 4H), 7.28 (t, J¼8.0 Hz, 2H); 13C
NMR (100 MHz, DMSO-d6):
d
¼16.3, 34.5, 73.7, 121.3, 122.2, 123.7,
129.1, 133.4, 143.2, 148.0 (CeB is not observed); 11B NMR (128 MHz,
DMSO-d6):
d
¼3.05; MS (m/z): 122 (14),153 (100),199 (38), 306 (70),
372 (Mꢀ, 65); HRMS (FABꢀ): m/z calcd for C23H23BNO3ꢀ: 372.1776;
found: 372.1776; elemental analysis: calcd (%) for C23H23BKNO3: C,
67.16; H, 5.64; N, 3.41; found: C, 62.82; H, 5.56; N, 2.96.
4.1.5. Potassium 4-(phenylethynyl)phenyltriolborate (1e). The syn-
thesis of potassium 4-(phenylethynyl)phenyl triolborate (1e) (85%)
using 4-(phenylethynyl)phenyl boronic acid29 was the same as the
synthesis of 2-naphthyl triolborate. 1H NMR (400 MHz, DMSO-d6):
3. Conclusions
We have demonstrated the efficiency of potassium triolborates
for double-coupling reaction of dibromo arenes, such as naphtha-
lene, biphenylene, dibenzothiophene, dibenzofuran, and xanthene.
Triolborates showed several advantages over boronic acids, in-
cluding high nucleophilicity of aryl groups for smooth trans-
metalation to a palladium catalyst and high solubility in organic
solvents, allowing the use of water-free solvents for preventing
hydrolytic BeC bond cleavage. We have developed a general
method for double-cross-coupling reaction of dibromo arenes.
d
¼0.50 (s, 3H), 3.60 (s, 6H), 7.19 (d, J¼8.4 Hz, 2H), 7.39 (q, J¼8.4,
10.8 Hz, 5H), 7.52 (d, J¼5.6 Hz, 2H); 13C NMR (100 MHz, DMSO-d6):
d
¼16.2, 34.5, 73.7, 87.3, 91.5, 117.4, 123.2, 128.1, 128.7, 128.8, 131.1,
132.4 (CeB is not observed); 11B NMR (128 MHz, DMSO-d6):
d¼1.30;
MS (m/z): 148 (100), 297 (36), 305 (Mꢀ, 25); HRMS (FABꢀ): m/z calcd
for C19H18BO3ꢀ: 305.1354; found: 305.1357; elemental analysis:
calcd (%) for C19H18BKO3: C, 66.29; H, 5.27; found: C, 55.63; H,4.53.
4.1.6. Potassium
4-((4-(diphenylamino)phenyl)
ethynyl)phenyl-
4. Experimental section
triolborate (1f). 4-((4-Bromophenyl)ethynyl)-N,N-diphenylaniline30
4.23 g (100 mmol) was dissolved in 100 mL THF and cooled to
ꢀ78 ꢁC under nitrogen. nBuLi (110 mmol) was added dropwise into
the reaction system at ꢀ78 ꢁC and stirred for 2 h at the same tem-
perature. Trimethyl borate (200 mmol) was added dropwise at
ꢀ78 ꢁC. After addition, the mixture was allowed to gradually warm to
room temperature overnight. Dilute HCl (2 M, 60 mL) was dropped
and stirred for 1 h. Dichloromethane was added and the layers sep-
arated. The aqueous layer was extracted with dichloromethane and
combined organic layers were washed with water, dried over MgSO4,
filtered, and the solvent evaporated under reduced pressure. The
crude solid was washed with hexane and dried under reduced
pressure to give desired boronic acid as a green-yellow solid (78%).1H
4.1. Synthesis of cyclic potassium aryltriolborates
4.1.1. Potassium 2-naphthyl triolborate (1a). 2-Naphthyl boronic
acid26 (100 mmol) and 1,1,1-tris(hydroxymethyl)ethane (100 mmol)
were dissolved in toluene (200 mL). Water was removed by azeo-
tropic distillation by the DeaneStark method for 4 h. After cooling to
room temperature, KOH (95 mmol) was added and heated at reflux
for 4 h by the DeaneStark method. The potassium 2-naphthyl tri-
olborate (1a) was precipitated. After cooling to room temperature,
the desired triolborate 1a (95%) was collected by filtration, washed
with diethyl ether, and dried under reduced pressure. 1H NMR
(400 MHz, DMSO-d6):
d¼0.53 (s, 3H), 3.62 (s, 6H), 7.25e7.31 (m, 2H),
NMR (400 MHz, CDCl3):
d¼7.02e7.15 (m, 8H), 7.29 (t, J¼8.0 Hz, 4H),

6808
G.-Q. Li et al. / Tetrahedron 67 (2011) 6804e6811
7.41 (d, J¼8.0 Hz, 2H), 7.61 (d, J¼8.0 Hz, 2H), 8.16 (d, J¼8.0 Hz, 2H); 13
C
(6), 315 (16), 330 (Mþ, 100); HRMS (EI): m/z calcd for C26H18
:
330.1409; found: 330.1401.
NMR (100 MHz, CDCl3):
d
¼88.9, 92.2, 115.8,122.2, 123.8, 125.2, 128.0,
129.5, 131.0, 132.8, 135.6, 147.2, 148.3 (CeB is not observed).
The synthesis of triolborate 1f (81%) was the same as the syn-
4.3.2. 2,3-Di(p-tolyl)thiophene (3bc). Oil; IR (neat): 3023, 2919,
thesis of 2-naphthyl triolborate. 1H NMR (400 MHz, DMSO-d6):
d
2862, 812 cmꢀ1; 1H NMR (400 MHz, CDCl3):
d
¼2.31 (s, 3H), 2.32 (s,
¼0.45 (s, 3H), 3.55 (s, 6H), 6.86 (d, J¼8.0 Hz, 2H), 7.02e7.12 (m, 8H),
3H), 7.06e7.11 (m, 5H), 7.16e7.20 (m, 4H), 7.25 (d, J¼5.2 Hz, 1H); 13C
7.29e7.35 (m, 8H); 13C NMR (100 MHz, DMSO-d6):
d
¼16.8, 35.0, 74.2,
NMR (100 MHz, CDCl3):
d
¼21.2, 21.2,123.6,128.9, 129.0, 129.1,129.1,
88.0, 91.1, 116.5, 118.4, 122.2, 124.4, 125.3, 129.2, 130.3, 132.8, 147.1,
130.5, 131.5, 133.7, 136.4, 137.1, 137.6, 138.3; MS (m/z): 117 (6), 189
(6), 202 (6), 215 (7), 234 (36), 249 (46), 264 (Mþ, 100); HRMS (EI):
m/z calcd for C18H16S: 264.0973; found: 264.0970.
147.6 (CeB and the other C are not observed); 11B NMR (128 MHz,
DMSO-d6):
d
¼2.98; MS (m/z): 122 (18),153 (100), 306 (50), 444 (14),
472 (Mꢀ, 50); HRMS (FABꢀ): m/z calcd for C31H27BNO3ꢀ: 472.2089;
found: 472.2087; elemental analysis: calcd (%) for C31H27BKNO3: C,
72.80; H, 5.32; N, 2.74; found: C, 67.27; H, 5.23; N, 2.27.
4.3.3. 2,3-Di(p-tolyl)furan (3bd). Oil; IR (neat): 3029, 2921, 2859,
1803, 1519, 1063, 819 cmꢀ1
;
1H NMR (400 MHz, CDCl3):
d¼2.32 (s,
3H), 2.37 (s, 3H), 6.51 (d, J¼2.0 Hz, 1H), 7.09 (d, J¼8.8 Hz, 2H), 7.15
4.1.7. Potassium 2-pyrenyltriolborate (1g)23. 4,4,5,5-Tetramethyl-2-
(2-pyrenyl)-1,3,2-dioxaborolane23,31 (3.28 g, 10 mmol), 1,1,1-tris
(hydroxymethyl)ethane (1.08 g, 9 mmol) and KOH (0.504 g,
9 mmol) were dissolve in 70 mL 1,4-dioxane. Water (0.5 mL) was
added. The mixture was warmed to 60 ꢁC and stirred for 16 h. After
cooling to room temperature the potassium pyrenyltriolborate (1g)
was collected by filtration, washed with diethyl ether, and dried
under reduced pressure (95%). 1H NMR (400 MHz, DMSO-d6):
(d, J¼7.6 Hz, 2H), 7.29 (d, J¼8.4 Hz, 2H), 7.41e7.45 (m, 3H); 13C NMR
(100 MHz, CDCl3):
d
¼20.8, 20.8, 113.4, 121.1, 125.7, 128.0, 128.1,
128.6, 128.8, 131.0, 136.2, 136.8, 140.7, 148.1; MS (m/z): 91 (24), 119
(36), 189 (9), 219 (38), 233 (16), 248 (Mþ, 100); HRMS (EI): m/z calcd
for C18H16O: 248.1201; found: 248.1200.
4.3.4. 1,8-Bis(p-tolyl)naphthalene (3be)34. UV: lmax (CHCl3)/nm (
dm3 molꢀ1 cmꢀ1) 241 (38,550), 303 (12,028); 1H NMR (400 MHz,
CDCl3):
¼2.21 (s, 6H), 6.71 (d, J¼7.6 Hz, 4H), 6.81 (d, J¼8.0 Hz, 4H),
7.40 (d, J¼6.8 Hz, 2H), 7.53 (t, J¼7.6 Hz, 2H), 7.92 (d, J¼8.4 Hz, 2H);
13C NMR (100 MHz, CDCl3):
3/
d
¼0.56 (s, 3H), 3.72 (s, 6H), 7.91e8.13 (m, 7H), 8.30 (s, 2H); 13C NMR
d
(100 MHz, DMSO-d6):
d
¼16.3, 34.7, 73.8, 122.4, 123.5, 124.6, 124.8,
125.1, 128.3, 130.4, 130.5 (CeB is not observed); 11B NMR (128 MHz,
d¼20.4, 124.6, 127.2, 127.9, 129.1, 129.2,
DMSO-d6):
d
¼1.72; MS (m/z): 122 (16), 153 (60), 238 (12), 328 (20),
130.2, 134.6, 134.9, 139.7, 140.1.
329 (Mꢀ, 100); HRMS (FABꢀ): m/z calcd for C21H18BO3ꢀ: 329.1354;
found: 329.1353; elemental analysis: calcd (%) for C21H18BKO3: C,
68.49; H, 4.93; found: C, 54.05; H, 4.91.
4.3.5. 4,6-Bis(p-tolyl)dibenzo[b,d]thiophene (3bf). Mp 96e97 ꢁC; IR
(neat): 1559, 1542, 1509 cmꢀ1
;
UV: lmax (CHCl3)/nm
dm3 molꢀ1 cmꢀ1) 251 (53,217), 326 (4374), 339 (5103); 1H NMR
(400 MHz, CDCl3):
¼2.40 (s, 6H), 7.26 (d, J¼8.1 Hz, 4H), 7.42e7.60
(m, 8H), 8.12e8.15 (m, 2H); 13C NMR (100 MHz, CDCl3):
(3/
4.2. General procedures for double-cross-coupling
d
d
¼21.3,
4.2.1. Pd(OAc)2/DMF/H2O system22a. The triolborate, dibromides
(0.2 mmol), and palladium acetate (10 mol %) were placed in a flask
under an atmosphere of nitrogen. DMF/H2O (4/1; 10 mL) was
added, and the reaction mixture was stirred at room temperature
for 16 h. The mixture was extracted with dichloromethane, dried
over MgSO4, and then purified by chromatography on silica gel.
120.4, 125.0, 126.9, 128.1, 129.5, 136.5, 136.9, 137.6, 137.7, 138.7; MS
(m/z): 69 (2), 182 (1), 364 (Mþ, 19); HRMS (EI): m/z calcd for
C26H20S: 364.1286; found: 364.1275.
4.3.6. 4,6-Bis(p-tolyl)dibenzo[b,d]furan (3bg). Mp 206e207 ꢁC; IR
(neat): 3027, 2914, 2853, 1516, 1484, 1395, 1185 cmꢀ1; UV: lmax
(CHCl3)/nm (
(sh) (10,104), 324 (sh) (9058); 1H NMR (400 MHz, CDCl3):
6H), 7.32 (d, J¼8.1 Hz, 4H), 7.43 (t, J¼8.1 Hz, 2H), 7.65 (dd, J¼2.7,
8.1 Hz, 2H), 7.87e7.96 (m, 6H); 13C NMR (100 MHz, CDCl3):
3
/dm3 molꢀ1 cmꢀ1) 261 (42,156), 294 (sh) (16,375), 313
4.2.2. Pd(OAc)2/CuCl system22d. The triolborate, dibromides
(0.2 mmol), palladium acetate (10 mol %), BIPHEP (11 mol), and
CuCl (0.4 equiv) were placed in a flask under an atmosphere of
nitrogen. DMF (15 mL) was added, and heated at 80 ꢁC for 14 h.
After cooling to room temperature, 15 mL water was added,
extracted with dichloromethane, dried over MgSO4, and then pu-
rified by chromatography on silica gel.
d¼2.45 (s,
d
¼21.3,
119.4, 123.3, 124.9, 125.6, 126.4, 128.5, 129.3, 133.3, 137.5, 153.3; MS
(m/z): 174 (5), 303 (2), 332 (2), 348 (Mþ, 100); HRMS (EI): m/z calcd
for C26H20O: 348.1514; found: 348.1506.
4.3.7. 1,8-Bis(p-tolyl)biphenylene (3bh). Mp 179e180 ꢁC; IR (neat):
4.2.3. Pd(PPh3)4/K2CO3
system. The triolborate, dibromides
1559, 1514 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1) 263
3
(0.2 mmol), Pd(PPh3)4 (10 mol %), and K2CO3 (2 equiv) were placed
in flask under an atmosphere of nitrogen. DMF (15 mL) was added,
and heated at 80 ꢁC for 14 h. After cooling to room temperature,
15 mL water was added, extracted with dichloromethane, dried
over MgSO4, and then purified by chromatography on silica gel.
(34,237), 356 (3938), 377 (3989); 1H NMR (400 MHz, CDCl3):
d
¼2.26
(s, 6H), 6.63e6.68 (m, 5H), 6.75e6.82 (m, 7H); 13C NMR (100 MHz,
CDCl3):
d
¼21.0, 115.4, 127.3, 128.0, 128.4, 129.2, 132.8, 135.0, 136.4,
148.2,151.3; MS (m/z): 150 (3), 302 (5), 316 (5), 332 (Mþ,100); HRMS
(EI): m/z calcd for C26H20: 332.1565; found: 332.1552.
4.3. Spectral data of diaryl arenes
4.3.8. 4,5-Bis(p-tolyl)-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene
(3bi). Mp 231e232 ꢁC; IR (neat): 2962, 2359, 1442, 1237, 815 cmꢀ1
;
The spectra of compounds 3ba,5d,32 3bb,33 3be,34 3ce,6c,7a and
3ge35 are identical to those reported in the literatures.
UV: lmax (CHCl3)/nm (3
/dm3 molꢀ1 cmꢀ1) 250 (24,632), 299 (6032);
1H NMR (400 MHz, CDCl3):
d
¼1.34 (s, 18H), 1.72 (s, 4H), 2.38 (s, 6H),
6.91 (d, J¼7.6 Hz, 4H), 7.12e7.19 (m, 6H), 7.41 (d, J¼2.4 Hz, 2H); 13C
4.3.1. 1,2-Di(2-naphthyl)benzene (3aa). Mp 97e98 ꢁC; IR (neat):
NMR (100 MHz, CDCl3):
d
¼20.7, 30.8, 31.1, 34.1, 34.8, 120.5, 125.4,
3053, 2925, 1734, 1505, 1489 cmꢀ1
;
1H NMR (400 MHz, CDCl3):
128.0, 128.9, 129.0, 130.1, 134.9, 135.3, 144.8, 145.8; MS (m/z): 222
(6), 236 (8), 397 (6), 471 (8), 487 (100), 502 (Mþ, 8); HRMS (EI): m/z
calcd for C37H42O: 502.3236; found: 502.3222.
d
¼7.06 (dd, J¼1.7, 8.5 Hz, 2H), 7.31e7.34 (m, 4H), 7.40 (dd, J¼3.6,
5.8 Hz, 2H), 7.43 (d, J¼8.5 Hz, 2H), 7.49 (dd, J¼3.6, 5.8 Hz, 2H),
7.62e7.67 (m, 4H), 7.73 (d, J¼1.7 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d
¼125.7, 125.9, 127.2, 127.6, 127.7, 128.0, 128.3, 128.4, 131.1, 132.0,
4.3.9. 1,8-Bis(4-biphenyl)naphthalene (3ce)6c,7a. UV: lmax (CHCl3)/
133.4, 139.2, 140.5; MS (m/z): 156 (10), 163 (12), 215 (6), 252 (2), 313
nm (3 )
/dm3 molꢀ1 cmꢀ1 242 (41,088), 304 (23,788); 1H NMR

G.-Q. Li et al. / Tetrahedron 67 (2011) 6804e6811
6809
(400 MHz, CDCl3):
d
¼7.03 (d, J¼8.1 Hz, 4H), 7.13 (d, J¼8.1 Hz, 4H),
lmax (CHCl3)/nm (
3
/dm3 molꢀ1 cmꢀ1) 272 (20,442), 308 (25,552),
7.22e7.32 (m,10H), 7.48(dd, J¼2.7, 8.1Hz, 2H), 7.55e7.60(m, 2H), 7.98
347 (20,442); 1H NMR (400 MHz, CDCl3):
d¼6.65 (t, J¼4 Hz, 2H),
(d, J¼8.1 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d¼125.2, 125.9, 126.8,
6.74 (d, J¼8 Hz, 4H), 6.83e6.89 (m, 8H), 6.97e7.01 (m, 4H), 7.06 (d,
127.1, 128.4, 128.7, 129.5, 130.3, 130.9, 135.4, 138.7, 140.1, 141.0, 142.2.
J¼8.4 Hz, 8H), 7.16 (t, J¼8 Hz, 8H); 13C NMR (100 MHz, CDCl3):
d
¼114.7, 121.6, 122.4, 124.4, 128.0, 128.1, 128.6, 128.9, 131.2, 131.8,
4.3.10. 4,6-Bis(4-biphenyl)dibenzo[b,d]thiophene (3cf). Mp 145e146
146.8, 147.1, 147.2, 150.8; MS (m/z): 319 (22), 638 (Mþ, 100); HRMS
(EI): m/z calcd for C48H34N2: 638.2722; found: 638.2727.
ꢁC; IR (neat): 3030, 1478, 1185 cmꢀ1; UV: lmax (CHCl3)/nm (
3/
dm3 molꢀ1 cmꢀ1) 263 (30,782), 292 (21,498), 341 (sh) (4397); 1H
NMR (400 MHz, CDCl3):
¼7.33e7.80 (m, 22H), 8.20 (dd, J¼2.7,
8.1 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d
4.3.17. 4,5-Bis[4-(diphenylamino)phenyl]-2,7-di-tert-butyl-9,9-
d
¼120.7, 125.2, 127.0, 127.1,
dimethyl-9H-xanthene (3di). Mp >300 ꢁC; IR (neat): 2958, 1592,
127.4, 127.5, 128.7, 128.8, 136.5, 136.6, 138.7, 139.4, 140.6, 140.8; MS
(m/z): 244 (23), 488 (Mþ, 100); HRMS (EI): m/z calcd for C36H24S:
488.1599; found: 488.1581.
1480, 1271 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1) 314
3
(27,509); 1H NMR (400 MHz, CDCl3):
d
¼6.91e6.99 (m, 8H),
7.04e7.06 (m, 8H), 7.12e7.16 (m, 8H), 7.20 (d, J¼2.4 Hz, 2H),
7.25e7.28 (m, 4H), 7.40 (d, J¼2.4 Hz, 2H); 13C NMR (100 MHz,
4.3.11. 4,6-Bis(4-biphenyl)dibenzo[b,d]furan (3cg). Mp 284e286 ꢁC;
IR (neat): 3028, 2159, 1478, 1394, 1181, 840 cmꢀ1; UV: lmax (CHCl3)/
CDCl3):
d
¼31.1, 31.1, 34.0, 34.7,120.6,121.9,122.2,124.2,125.6,128.4,
128.8, 130.0, 130.1, 131.9, 144.8, 145.6, 145.9, 147.2; MS (m/z): 381
(8), 396 (56), 777 (8), 793 (75), 808 (Mþ, 100); HRMS (EI): m/z calcd
for C59H56N2O: 808.4393; found: 808.4379.
nm (
¼7.36e7.40 (m, 2H), 7.46e7.50 (m, 6H), 7.68e7.76 (m, 10H),
7.99e8.10 (m, 6H); 13C NMR (100 MHz, CDCl3):
3
/dm3 molꢀ1 cmꢀ1) 282 (36,863); 1H NMR (400 MHz, CDCl3):
d
d¼119.3, 123.0,
124.5, 124.7, 126.2, 126.6, 126.7, 126.9, 126.9, 128.4, 128.5, 134.7,
140.3, 152.9; MS (m/z): 236 (30), 289 (8), 306 (40), 320 (55), 400
(10), 472 (Mþ, 100); HRMS (EI): m/z calcd for C36H24O: 472.1827;
found: 472.1815.
4.3.18. 1,8-Bis[4-(phenylethynyl)phenyl] naphthalene (3ee). Mp
229e230 ꢁC; IR (neat): 2360, 2340, 1507, 1180, 821 cmꢀ1; UV: lmax
(CHCl3)/nm (
NMR (400 MHz, CDCl3):
(m, 8H), 7.42e7.45 (m, 6H), 7.56e7.61 (m, 4H), 7.97 (dd, J¼1.2,
8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3):
¼88.6, 89.1, 120.3, 123.0,
3
/dm3 molꢀ1 cmꢀ1) 280 (15,860), 314 (17,302); 1H
d
¼6.95 (dd, J¼1.6 Hz, 6.4 Hz, 4H), 7.15e7.25
4.3.12. 4,5-Di(4-biphenyl)-2,7-di-tert-butyl-9,9-dimethyl-9H-xan-
d
thene (3ci). Mp 255e256 ꢁC; IR (neat): 2961, 2360, 1437, 1231,
124.8, 127.4, 127.7, 128.5, 128.6, 129.2, 130.0, 131.1, 134.9, 139.1,
835 cmꢀ1; UV: lmax (CHCl3)/nm (
3
/dm3 molꢀ1 cmꢀ1) 269 (40,122),
142.5; MS (m/z): 480 (Mþ, 100); HRMS (EI): m/z calcd for C38H24
:
304 (sh) (16,926); 1H NMR (400 MHz, CDCl3):
6H), 7.23e7.28 (m, 8H), 7.34e7.43 (m, 12H), 7.46 (d, J¼2.4 Hz, 2H);
13C NMR (100 MHz, CDCl3):
d¼1.37 (s,18H),1.75 (s,
480.1878; found: 480.1865.
d¼30.9, 31.1, 34.1, 34.8, 121.0, 125.7, 126.1,
4.3.19. 4,6-Bis[4-(phenylethynyl)phenyl]dibenzo[b,d]thiophene
126.5, 128.3, 128.3, 129.7, 130.3, 136.9, 138.8, 140.3, 145.0, 145.8; MS
(m/z): 262 (3), 284 (8), 305 (25), 595 (8), 611 (100), 626 (Mþ, 8);
HRMS (EI): m/z calcd for C47H46O: 626.3549; found: 626.3526.
(3ef). Mp 238e240 ꢁC; IR (neat): 3033, 2360, 2339, 2159, 1518,
1397, 1179, 1065, 840 cmꢀ1
;
UV: lmax (CHCl3)/nm
(3/
dm3 molꢀ1 cmꢀ1) 277 (33,275), 303 (39,716); 1H NMR (400 MHz,
CDCl3):
d
¼7.33e7.36 (m, 6H), 7.49e7.60 (m, 8H), 7.64e7.72 (m, 8H),
4.3.13. 1,8-Bis[4-(diphenylamino)phenyl] naphthalene (3de). Mp
278e279 ꢁC; IR (neat): 3027, 1588, 1489, 1271, 815 cmꢀ1; UV: lmax
8.19 (dd, J¼1.2, 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3):
¼89.3,
d
90.3, 121.0, 123.1, 123.3, 125.4, 127.0, 128.4, 128.5, 131.8, 132.2, 136.3,
136.7, 138.6, 140.4; MS (m/z): 268 (21), (Mþ, 100); HRMS (EI): m/z
calcd for C40H24S: 536.1599; found: 536.1589.
(CHCl3)/nm (
NMR (400 MHz, CDCl3):
3
/dm3 molꢀ1 cmꢀ1) 313 (13,526), 337 (12,296); 1H
d¼6.84 (dd, J¼8.4, 15.6 Hz, 8H), 7.01 (t,
J¼6.8 Hz, 4H), 7.17e7.25 (m, 16H), 7.43 (d, J¼6.8 Hz, 2H), 7.53 (t,
J¼7.6 Hz, 2H), 7.91 (d, J¼8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
4.3.20. 4,6-Bis[4-(phenylethynyl)phenyl]dibenzo[b,d]furꢀa1n
;
d
¼121.0, 122.9, 125.0, 125.1, 128.1, 129.2, 129.4, 130.5, 135.6, 137.1,
(3eg). Mp 198e200 ꢁC; IR (neat): 3050, 2159, 1511, 1106, 844 cm
140.2, 145.7, 147.7; MS (m/z): 77 (2), 167 (4), 307 (13), 614 (Mþ, 100);
HRMS (EI): m/z calcd for C46H34N2: 614.2722; found: 614.2717.
UV: lmax (CHCl3)/nm (
(400 MHz, CDCl3):
¼7.35e7.39 (m, 6H), 7.47 (t, J¼7.6 Hz, 2H),
7.58e7.61 (m, 4H), 7.69e7.71 (m, 6H), 7.97e7.80 (m, 6H); 13C NMR
(100 MHz, CDCl3):
124.9, 126.6, 128.3, 128.4, 128.5, 131.7, 131.9, 136.0, 153.2; MS (m/z):
260 (19), 442 (4), 520 (Mþ, 100); HRMS (EI): m/z calcd for C40H24O:
520.1827; found: 520.1804.
3
/dm3 molꢀ1 cmꢀ1) 299 (84,377); 1H NMR
d
4.3.14. 4,6-Bis[4-(diphenylamino)phenyl]dibenzo[b,d]thiophene
d
¼89.4, 90.3, 120.1, 122.7, 123.3, 123.5, 124.9,
(3df). Mp 204e205 ꢁC; IR (neat): 3033, 1585, 1483, 1270, 1179,
746 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1) 298 (24,152),
3
312 (24,152), 344 (sh) (20,127); 1H NMR (400 MHz, CDCl3):
¼7.04e7.08 (m, 4H), 7.16e7.31 (m, 20H), 7.47e7.61 (m, 8H),
8.13e8.16 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
d¼119.8, 122.6,
4.3.21. 4,5-Bis[4-(phenylethynyl)phenyl]-2,7-di-tert-butyl-9,9-
122.7, 124.4, 124.6, 126.4, 128.5, 128.9, 133.6, 136.1, 136.1, 137.9, 147.1,
147.1; MS (m/z): 335 (32), 670 (Mþ, 100); HRMS (EI): m/z calcd for
C48H34N2S: 670.2443; found: 670.2423.
dimethyl-9H-xanthene (3ei). Mp 242e243 ꢁC; IR (neat): 3058, 1516,
1179 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1) 291 (40,494);
3
1H NMR (400 MHz, CDCl3):
(m, 4H), 7.20e7.23 (m, 6H), 7.25e7.40 (m, 10H), 7.45 (d, J¼2.0 Hz,
2H), 7.61 (s, 2H); 13C NMR (100 MHz, CDCl3):
d¼1.36 (s, 18H), 1.73 (s, 6H), 7.12e7.14
4.3.15. 4,6-Bis[4-(diphenylamino)phenyl]dibenzo[b,d]furan
d¼31.3, 31.6, 34.6, 35.2,
(3dg). Mp 255e256 ꢁC; IR (neat): 1589, 1488, 1265 cmꢀ1; UV: lmax
89.4, 89.5, 121.6, 121.6, 123.4, 125.8, 126.9, 127.8, 128.1, 128.4, 128.6,
129.6, 130.7, 131.1,131.6,131.6,132.1,138.1,145.6,146.1; MS (m/z): 43
(12), 50 (25), 57 (17), 76 (42), 83 (20), 203 (25), 230 (100), 262 (71),
329 (14), 659 (100), 674 (Mþ, 29); HRMS (EI): m/z calcd for C51H46O:
674.3549; found: 674.3549.
(CHCl3)/nm (
NMR (400 MHz, CDCl3):
7.42 (t, J¼8.0 Hz, 2H), 7.64 (d, J¼7.6 Hz, 2H), 7.86 (d, J¼8.8 Hz, 4H),
7.91e7.93 (m, 2H); 13C NMR (100 MHz, CDCl3):
3
/dm3 molꢀ1 cmꢀ1) 302 (28,156), 346 (19,644); 1H
d¼7.00e7.03 (m, 4H), 7.16e7.25 (m, 20H),
d¼118.7,122.6,122.8,
124.1, 124.4, 124.7, 125.4, 128.8, 128.8, 129.4, 147.0, 147.1, 152.7; MS
(m/z): 411 (4), 488 (6), 654 (Mþ, 100); HRMS (EI): m/z calcd for
C48H34N2O: 654.2671; found: 654.2660.
4.3.22. 1,8-Bis[4-((4-(diphenylamino)phenyl) ethynyl)phenyl]naph-
thalene (3fe). Mp 274e275 ꢁC; IR (neat): 30,323, 2358, 1586, 1510,
1487, 1268, 820 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1
3 )
4.3.16. 1,8-Bis[4-(diphenylamino)phenyl]biphenylene
(3dh). Mp
306 (44,825), 352 (63,570); 1H NMR (400 MHz, CDCl3):
(m, 8H), 7.02e7.07 (m, 12H), 7.12e7.14 (m, 4H), 7.20e7.24 (m, 8H),
d
¼6.90e7.0
298e299 ꢁC; IR (neat): 2360, 2185, 1588, 1489, 1067, 831 cmꢀ1; UV:

6810
G.-Q. Li et al. / Tetrahedron 67 (2011) 6804e6811
7.32 (dd, J¼2.0, 6.8 Hz, 4H), 7.42 (dd, J¼1.6, 7.2 Hz, 2H), 7.56 (dd,
J¼7.2, 8.4 Hz, 2H), 7.95 (dd, J¼1.6, 8.4 Hz, 2H); 13C NMR (100 MHz,
(36,037), 313 (33,258), 325 (36,873), 342 (25,305); 1H NMR
(400 MHz, CDCl3):
d
¼1.43 (s, 18H), 1.88 (s, 6H), 7.11 (s, 8H), 7.40 (d,
CDCl3):
d
¼88.5, 88.9, 116.1, 120.7, 122.0, 122.9, 124.3, 124.8, 128.4,
J¼2.4 Hz, 2H), 7.55e7.68 (m, 8H), 7.87 (s, 4H); 13C NMR (100 MHz,
128.6, 128.9, 129.2, 129.9, 130.4, 132.1, 135.0, 139.2, 142.2, 146.7,
147.1; MS (m/z): 407 (30), 814 (Mþ, 100); HRMS (EI): m/z calcd for
C62H42N2: 814.3348; found: 814.3547.
CDCl3):
d
¼31.2, 32.4, 34.2, 34.6, 121.7, 122.6, 123.5, 123.7, 124.7,
125.4, 125.6, 125.7, 126.2, 129.1, 129.2, 129.8, 129.9, 134.9, 144.9,
145.0; MS (m/z): 338 (12), 353 (48), 707 (100), 722 (Mþ, 100); HRMS
(EI): m/z calcd for C55H46O: 722.3549; found: 722.3548.
4.3.23. 4,6-Bis[4-((4-(diphenylamino)phenyl) ethynyl)phenyl]dibenzo
[b,d]thiophene (3ff). Mp 194e196 ꢁC; IR (neat): 3033, 2358, 1585,
Acknowledgements
1489, 1271, 1181, 836 cmꢀ1
;
UV: lmax (CHCl3)/nm
dm3 molꢀ1 cmꢀ1) 273 (43,555), 299 (47,039), 361 (67,075); 1H NMR
(400 MHz, CDCl3):
(3/
This work was supported in part by the Global COE Program
(Project No. B01, Catalysis as the Basis for Innovation in Materials
Science) from the Ministry of Education, Culture, Sports, Science,
and Technology, Japan.
d
¼7.01e7.08 (m, 8H), 7.11e7.13 (m, 8H), 7.25e7.39
(m, 8H), 7.38e7.40 (m, 4H), 7.49e7.51 (m, 2H), 7.55e7.63 (m, 6H),
7.68e7.70 (m, 4H), 7.18 (dd, J¼1.2, 8.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3):
d
¼88.0, 90.1, 115.6, 120.4, 121.8, 122.9, 123.1, 124.5, 124.8,
126.5, 127.8, 128.9, 131.4, 132.1, 135.8, 136.1, 138.0, 139.4, 146.7, 147.5;
MS (m/z): 435 (30), 870 (Mþ, 100); HRMS (EI): m/z calcd for
C64H42N2O: 870.3069; found: 870.3074.
References and notes
1. For reviews, see: (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457e2483; (b)
Suzuki, A. In Metal-catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J.,
Eds.; Wiley-VCH: Weinheim, 1998; pp 49e98; (c) Miyaura, N. In Advances in
Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI: Stamford, 1998; Vol. 6, p 187;
(d) Miyaura, N. In Topics in Current Chemistry; 2002; Vol. 219, p 11; (e) Suzuki,
A.; Brown, H. C. Organic Synthesis via Boranes. Suzuki Coupling; Aldrich
Chemical: Milwaukee, 2003; Vol. 3; (f) Miyaura, N. In Metal-catalyzed Cross-
Coupling Reactions, Second, Completely Revised and Enlarged Edition; de Mei-
jere, A., Diederich, F., Eds.; Wiley-VCH: 2005; pp 41e124.
4.3.24. 4,6-Bis[4-((4-(diphenylamino)phenyl) ethynyl)phenyl]dibenzo
[b,d]furan (3fg). Mp 124e125 ꢁC; IR (neat): 3032, 2359, 1586, 1511,
1488, 1271, 834, 693 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1
3 )
298 (63,270), 362 (74,385); 1H NMR (400 MHz, CDCl3):
d
¼7.01e7.13
(m, 8H), 7.24e7.27 (m, 8H), 7.27e7.29 (m, 8H), 7.41e7.46 (m, 6H),
7.64e7.68 (m, 6H), 7.94e7.60 (m, 6H); 13C NMR (100 MHz, CDCl3):
2. (a) Hassan, J.; Svignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002,
102, 1359e1469; (b) Bringmann, G.; Gulder, T.; Gulder, T. A. M.; Breuning, M.
Chem. Rev. 2011, 111, 563e639.
d
¼88.3, 90.2,115.6,119.6,121.9, 122.6, 123.1,124.5,124.5,126.0,128.0,
131.3, 132.2, 135.2, 146.7, 147.5, 152.7; MS (m/z): 427 (35), 854 (Mþ,
100); HRMS (EI): m/z calcd for C64H42N2O: 854.3297; found:
854.3294.
3. (a) Peeira, R.; Iglesias, B.; de Lera, A. R. Tetrahedron 2001, 57, 7871e7881; (b)
€
Schroter, S.; Stock, C.; Bach, T. Tetrahedron 2005, 61, 2245e2267.
4. (a) Handy, S. T.; Sabatini, J. J. Org. Lett. 2006, 8, 1537e1539; (b) Handy, S. T.;
Mayi, D. Tetrahedron Lett. 2007, 48, 8108e8110; (c) Handy, S. T.; Wilson, T.;
Muth, A. J. Org. Chem. 2007, 72, 8496e8500; (d) Varello, S.; Handy, S. T. Syn-
thesis 2009, 138e142; (e) Dong, C.-G.; Liu, T.-P.; Hu, Q.-S. Synlett 2009,
1081e1086; (f) Toguem, S.-M. T.; Villinger, A.; Langer, P. Synlett 2010, 909e912;
(g) Hung, N. T.; Hussain, M.; Malik, I.; Villinger, A.; Langer, P. Tetrahedron Lett.
2010, 51, 2420e2422; (h) Piala, A.; Mayi, D.; Handy, S. T. Tetrahedron 2011, 67,
4147e4154.
5. (a) Berthiol, F.; Kondolff, I.; Doucet, H.; Santelli, M. J. Organomet. Chem. 2004,
689, 2786e2798; (b) Sinclair, D. J.; Shrburn, M. S. J. Org. Chem. 2005, 70,
3730e3733; (c) Dong, C.-G.; Hu, Q.-S. J. Am. Chem. Soc. 2005, 127, 10006e10007;
(d) Liu, L.; Zhang, Y.; Xin, B. J. Org. Chem. 2006, 71, 3994e3997; Lee, D.-H.; Jin,
M.-J. Org. Lett. 2011, 13, 252e255.
4.3.25. 4,5-Bis[4-((4-(diphenylamino)phenyl) ethynyl)phenyl]-2,7-
di-tert-butyl-9,9-dimethyl-9H-xanthene (3fi). Mp 243e244 ꢁC; IR
(neat): 2956, 2358, 2155, 2024, 1588, 1490, 1441, 1274, 1234,
834 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1) 282 (39,363),
3
351 (63,586); 1H NMR (400 MHz, CDCl3):
d
¼1.36 (s, 18H), 1.72 (s,
6H), 6.83 (d, J¼6.8 Hz, 4H), 6.84e7.03 (m, 12H), 7.17e7.21 (m, 10H),
7.24e7.26 (m, 4H), 7.30e7.33 (m, 8H), 7.44 (d, J¼2.0 Hz, 2H); 13C
NMR (100 MHz, CDCl3):
d
¼31.6, 31.6, 34.6, 35.3, 89.0, 89.7, 116.7,
121.5, 121.9, 122.4, 123.3, 124.8, 125.7, 128.7, 129.3, 129.6, 130.7,
131.0, 132.7, 137.8, 145.6, 146.1, 147.2, 147.5; MS (m/z): 412 (7), 496
(27), 993 (67), 1008 (Mþ, 100); HRMS (EI): m/z calcd for C75H64N2O:
1008.5019; found: 1008.4974.
6. (a) Thirsk, C.; Hawkes, G. E.; Kroemer, R. T.; Liedl, K. R.; Loertig, T.; Nasser, R.;
Pritchard, R. G.; Steele, M.; Warren, J. E.; Whiting, A. J. Chem. Soc., Perkin Trans. 2
2002, 1510e1519; (b) Pieters, G.; Terrasson, V.; Gaucher, A.; Prim, D.; Marrot, J.
Eur. J. Org. Chem. 2010, 5800e5806; (c) Lima, CF. R. A. C.; Rodriguez-Borges, J. E.;
Santos, LM. N. B. F. Tetrahedron 2011, 67, 689e697.
7. (a) Ibuki, E.; Ozasa, S.; Fujioka, Y.; Mizutani, H. Bull. Chem. Soc. Jpn. 1982, 55,
845e851; (b) Kuroda, M.; Nakayama, J.; Hoshino, M. Tetrahedron 1993, 49,
3735e3748.
8. Iyoda, M.; Kondo, T.; Nakano, K.; Hara, K.; Kuwatani, Y.; Yoshida, M.; Mat-
suyama, H. Org. Lett. 2000, 2, 2081e2083.
4.3.26. 1,8-Bis(2-pyrenyl)naphthalene (3ge)35. UV: lmax (CHCl3)/nm
(3
/dm3 molꢀ1 cmꢀ1) 245 (49,688), 278 (24,844), 315 (21,144), 328
(27,487), 344 (sh) (11,629); 1H NMR (400 MHz, CD2Cl2):
9. (a) House, H. O.; Campbell, W. J.; Gall, M. J. Org. Chem. 1970, 35, 1815e1819; (b)
Clough, R. L.; Roberts, J. D. J. Am. Chem. Soc. 1976, 98, 1018e1020; (c) Clough, R.
L.; Kung, W. J.; Marsh, R. E.; Roberts, J. D. J. Org. Chem. 1976, 41, 3603e3609; (d)
d
¼7.28e7.34 (m, 8H), 7.55e7.61 (m, 10H), 7.68e7.70 (m, 4H), 8.14
(dd, J¼2.4, 6.8 Hz, 2H); 13C NMR (100 MHz, CDCl3):
¼122.3, 123.6,
d
124.5,125.6,126.4,126.6,126.9,129.6,130.0,130.7,131.6,140.7,141.4
(three carbons were not observed); MS (m/z): 264 (13), 326 (23),
528 (Mþ, 100); HRMS (EI): m/z calcd for C42H24: 528.1870; found:
528.1863.
€
Gerson, F.; Heckendon, R.; Mockel, R. J. Chem. Soc., Chem. Commun. 1985, 689;
€
€
(e) Gerson, F.; Heckendorn, R.; Mockel, R.; Vogtle, F. Helv. Chim. Acta 1985, 68,
ꢀ
1923e1932; (f) Yang, Z.-Z.; Kovac, B.; Heilbronner, E.; Lecoultre, J.; Chan, C. W.;
Wong, H. N. C.; Hopf, H.; Vogtle, F. Helv. Chim. Acta 1987, 70, 299e307; (g) Cozzi,
€
F.; Cinquini, M.; Annunziata, R.; Dwyer, T.; Siegel, J. S. J. Am. Chem. Soc. 1992, 114,
5729e5733; (h) Cozzi, F.; Ponzini, F.; Annunziata, R.; Cinquini, M.; Seigel, J. S.
Angew. Chem., Int. Ed. Engl. 1995, 34, 1019e1020; (i) Cozzi, F.; Siegel, J. S. Pure
Appl. Chem. 1995, 67, 683e689.
4.3.27. 1,8-Bis(2-pyrenyl)biphenylene (3gh). Mp >300 ꢁC; IR (neat):
3037, 2360, 1362, 1257, 876 cmꢀ1; UV: lmax (CHCl3)/nm (
3/
€
10. (a) Leppkes, R.; Vogtle, F.; Leppertz, F. Chem. Ber. 1982, 115, 926e933; (b) Lep-
dm3 molꢀ1 cmꢀ1) 277 (73,509), 328 (28,740), 344 (22,661), 382 (sh)
(4974); 1H NMR (400 MHz, CD2Cl2):
¼6.84e7.00 (m, 2H),
7.02e7.07 (m, 6H), 7.13e7.25 (m, 6H), 7.46e7.54 (m, 10H); 13C NMR
(100 MHz, CDCl3):
€
€
pkes, R.; Vogtle, F. Chem. Ber. 1983, 116, 215e219; (c) Vogtle, F.; Papkalla, T.;
Koch, H.; Nieger, M. Chem. Ber. 1990, 123, 1097e1103; (d) Sabater, L.; Guillot, R.;
Aukauloo, A. Tetrahedron Lett. 2005, 46, 2923e2926; (e) Sabater, Lachaud, F.;
Hureau, C.; Aukauloo, A. Tetrahedron Lett. 2006, 47, 569e571; (f) Ghosn, M.;
Wolf, C. Tetrahedron 2010, 66, 3989e3994.
d
d
¼115.9, 123.2, 123.3, 123.7, 123.9, 125.2, 125.8,
11. (a) Wolf, C.; Mei, X. J. Am. Chem. Soc. 2003, 125, 10651e10658; (b) Tu-
mambac, G. E.; Wolf, C. J. Org. Chem. 2004, 69, 2048e2055; (c) Mei, X.; Wolf,
C. J. Org. Chem. 2005, 70, 2299e2305; (d) Tumambac, G. E.; Wolf, C. J. Org.
Chem. 2005, 70, 2930e2938; (e) Mei, X.; Martin, R. M.; Wolf, C. J. Org. Chem.
2006, 71, 2854e2861; (f) Mei, X.; Wolf, C. Tetrahedron Lett. 2006, 47,
7901e7904.
12. (a) Liu, X. Y.; Bai, D. R.; Wang, S. Angew. Chem., Int. Ed. 2006, 45, 5475e5478; (b)
Zhao, S.-B.; Wucher, P.; Hudson, Z. M.; MacCormick, T. M.; Liu, X.-Y.; Wang, S.;
Feng, X.-D.; Lu, Z.-H. Organometallics 2008, 27, 6446e6456.
126.1, 128.9, 129.8, 130.1, 133.4, 135.3, 149.2, 151.7 (one carbon was
not observed); MS (m/z): 274 (13), 350 (4), 552 (Mþ, 100); HRMS
(EI): m/z calcd for C44H24: 552.1870; found: 552.1866.
4.3.28. 4,5-Bis(2-pyrenyl)-2,7-di-tert-butyl-9,9-dimethyl-9H-xan-
thene (3gi). Mp >300 ꢁC; IR (neat): 2957, 2361, 2163, 1440, 1257,
879, 713 cmꢀ1; UV: lmax (CHCl3)/nm ( /dm3 molꢀ1 cmꢀ1) 263
3

G.-Q. Li et al. / Tetrahedron 67 (2011) 6804e6811
6811
13. (a) Iwahori, F.; Hatano, S.; Abe, J. J. Phys. Org. Chem. 2007, 20, 857e863; (b)
Fujita, K.; Hatano, S.; Kato, D.; Abe, J. Org. Lett. 2008, 10, 3105e3108.
14. (a) Lanazzi, L.; Mancinelli, M.; Mazzanti, A. J. Org. Chem. 2007, 72,
10045e10050; (b) Lunazzi, L.; Mancinelli, M.; Mazzanti, A. J. Org. Chem. 2008,
73, 2198e2205; (c) Cozzi, F.; Annunziata, R.; Benaglia, M.; Baldridge, K. K.;
Aguirre, G.; Estrada, J.; Sritana-Anant, Y.; Siegel, J. S. Phys. Chem. Chem. Phys.
2008, 10, 2686e2694.
20. (a) Hunter, C. A. J. Mol. Biol. 1991, 218, 837e846; (b) Hunter, C. A. J. Mol. Biol.
1993, 230, 1025e1054; (c) Mignon, P.; Loverix, S.; Steyaert, J.; Geerlings, P.
Nucleic Acids Res. 2005, 33, 1779e1789.
21. (a) Dahl, T. Acta Chem. Scand. 1994, 48, 95e106; (b) Williams, J. H. Acc. Chem. Res.
1993, 26, 593e598.
22. (a) Yamamoto, Y.; Takizawa, M.; Yu, X.-Q.; Miyaura, N. Angew. Chem., Int. Ed. 2008,
47, 928e931; (b) Yamamoto, Y.; Takizawa, M.; Yu, X.-Q.; Miyaura, N. Heterocycles
2010, 80, 359e368; (c) Yamamoto, Y.;Sugai, J.; Takizawa, M.;Miyaura, N. Org. Synth.
2011, 88, 79e86; (d) Li, G.-Q.; Yamamoto, Y.; Miyaura, N. Synlett, 2011, 1769–1773.
23. Li, G.-Q.; Kiyomura, S.; Yamamoto, Y.; Miyaura, N. Chem. Lett. 2011, 40, 702e703.
24. Yu, X.-Q.; Yamamoto, Y.; Miyaura, N. Chem.dAsian J. 2008, 3, 1517e1522.
25. (a) Yu, X.-Q.; Yamamoto, Y.; Miyaura, N. Synlett 2009, 994e998; (b) Yu, X.-Q.;
Shirai, T.; Yamamoto, Y.; Miyaura, N. Chem.dAsian J. 2011, 6, 932e937.
26. Wipf, P.; Jung, J.-K. J. Org. Chem. 2000, 65, 6319e6337.
27. Bhongale, C. J.; Hsu, C.-S. Angew. Chem., Int. Ed. 2006, 45, 1404e1408.
28. Wu, W.; Cheng, C.; Wu, W.; Guo, H.; Ji, S.; Song, P.; Han, K.; Zhao, J.; Zhang, X.;
Wu, Y.; Du, G. Eur. J. Inorg. Chem. 2010, 4683e4696.
29. Shen, X.; Ho, D. M.; Pascal, R. A., Jr. J. Am. Chem. Soc. 2004, 126, 5798e5805.
30. Fang, J.-K.; An, D.-L.; Wakamatsu, K.; Ishikawa, T.; Iwanaga, T.; Toyota, S.;
Matsuo, D.; Orita, A.; Otera, J. Tetrahedron Lett. 2010, 51, 917e920.
31. (a) Coventry, D. N.; Batsanov, A. S.; Goeta, A. E.; Howard, J. A. K.; Marder, T. B.;
15. Hasegawa, A.; Ishikawa, T.; Ishihara, K.; Yamamoto, H. Bull. Chem. Soc. Jpn. 2005,
78, 1401e1410.
16. Kumazoe, K.; Arima, K.; Mataka, S.; Walton, D.; Thiemann, T. J. Chem. Res.,
Miniprint 2003, 245e248.
17. (a) Breinlinger, E. C.; Rotello, V. M. J. Am. Chem. Soc. 1997, 119, 1165e1166; (b)
Zeng, F.; Zimmerman, S.; Kolotuchin, S. V.; Reichert, D. E. C.; Ma, Y. Tetrahedron
2002, 58, 825e843; (c) Liu, S.-Y.; Nocera, D. G. J. Am. Chem. Soc. 2005, 127,
5278e5279; (d) Yang, J. Y.; Bachmann, J.; Nocera, D. G. J. Org. Chem. 2006, 71,
8706e8714; (e) Yang, J. Y.; Nocera, D. G. J. Am. Chem. Soc. 2007, 129, 8192e8198;
(f) Develay, S.; Williams, J. A. G. Dalton Trans. 2008, 4562e4564; (g) Tong, W.-L.;
Chan, M. C. W.; Yiu, S.-M. Organometallics 2010, 29, 6377e6383.
18. (a) Hunter, C. A. Chem. Soc. Rev. 1994, 101e109; (b) Philip, D.; Stoddart, J. F.
Angew. Chem., Int. Ed. 1996, 35, 1154e1196; (c) Glaessens, C. G.; Stoddart, F.
J. Phys. Org. Chem. 1997, 10, 254e272; (d) Hunter, C. A.; Lawson, K. R.; Perkins, J.;
Urch, C. J. J. Chem. Soc., Perkin Trans. 2 2001, 651e669; (e) Davis, J. T.; Spada, G. P.
Chem. Soc. Rev. 2007, 36, 296e313; (f) Tewari, A. K.; Dubey, R. Bioorg. Med. Chem.
2008, 16, 126e143; (g) Klosterman, J. K.; Yamauchi, Y.; Fujita, M. Chem. Soc. Rev.
2009, 38, 1714e1725; (h) Kuruppannan, S.; Chambron, J.-C. Chem.dAsian J.
2011, 6, 964e984.
Perutz, R. N. Chem. Commun. 2005, 2172e2174; (b) Wanninger-Wei
Wagenknecht, H.-A. Eur. J. Org. Chem. 2008, 64e71.
b, C.;
32. Yoshida, H.; Okada, K.; Kawashima, S.; Tanino, K.; Oshita, J. Chem. Commun.
2010, 1763e1765.
33. Spinella, S. M.; Guan, Z.-H.; Chen, J.; Zhang, X. Synthesis 2009, 3094e3098.
34. Clough, R. L.; Mison, P.; Roberts, J. D. J. Org. Chem. 1976, 41, 2252e2255.
35. Wahl, P.; Krieger, C.; Schweitzer, D.; Staab, H. A. Chem. Ber. 1984, 117, 260e276.
19. (a) Jones, G. B. Tetrahedron 2001, 57, 7999e8016; (b) Ghosn, M. W.; Wolf, C.
J. Org. Chem. 2010, 75, 6653e6659.