Palladium-Catalyzed Double-Suzuki-Miyaura Reactions Using Cyclic Dibenziodoniums: Synthesis of o-Tetraaryls

Article abstract of DOI:10.1021/acs.joc.5b02255

Palladium-catalyzed double-Suzuki-Miyaura couplings between cyclic dibenziodoniums and arylboronic acids have been developed. As such, a wide range of o-tetraaryls were synthesized in good to excellent yields of 22-94%. Furthermore, tetraphenylene was pre

Full text of DOI:10.1021/acs.joc.5b02255

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Featured Article
Palladium Catalyzed Double Suzuki-Miyaura Reactions Using
Cyclic Dibenziodoniums: Synthesis of ortho-Tetraaryls
Yanxia Zhang, Jianwei Han, and Zhen-Jiang Liu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b02255 • Publication Date (Web): 26 Nov 2015
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Palladium Catalyzed Double Suzuki-Miyaura
Reactions Using Cyclic Dibenziodoniums: Synthesis
of ortho-Tetraaryls
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Yanxia Zhang,a,b Jianwei Han*b and Zhen-Jiang Liu*a
Address: aSchool of Chemical and Environmental Engineering, Shanghai Institute of
Technology, 100 Haiquan Road, Shanghai 201418, P. R. China and bShanghai–Hong
Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic
Chemistry, The Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032,
P. R. China.
Email: Jianwei Han – jianweihan@sioc.ac.cn; Zhen-Jiang Liu – zjliu@sit.edu.cn
* Corresponding author
Abstract
Palladium catalyzed double Suzuki-Miyaura couplings between cyclic
dibenziodoniums and arylboronic acids have been developed. As such, a wide range
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of ortho-tetraaryls were synthesized in good to excellent yields of 22-94%.
Furthermore, tetraphenylene was prepared in 21% isolated yield with
2,2’-biphenyldiboronic acid by using this method.
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Introduction
ortho-tetraaryls are advantageous building blocks for the construction of
specific polyaromatic hydrocarbons (PAHs)1, which were now well-established
as functional materials (A-B, Figure 1)2 or catalyst ligands ( , Figure 1).3
C
Furthermore, ortho-oligoaryls were identified to adopt a helical conformation,
leading to applications as three-dimensional scaffolds in the study of steric
interactions along the rigid backbone.4 With regard to the preparation of
ortho-oligoaryls, mono-Suzuki-Miyaura couplings between the biphenyl
derivatives are well recorded (1. Mono-coupling, Figure 1).5 however, the
availability of starting materials is very limited. On the other hand, double
coupling reaction is very versatile and thus therefore generally employed in the
synthesis of polyaromatic compounds.6 In this context, double Suzuki-Miyaura
couplings between dihaloaryls and two molecules of arylboric acids, or diboron
compounds with two molecules of arylhalogens, have been reported.7
Surprisingly, dihalobiphenyls as Suzuki-Miyaura coupling parters were rarely
studied. López-Romero employed p-dibromobiphenyl derivatives in coupling
reactions; but mono-coupling products were preferentially obtained.8 Very
recently, Li and Wang reported double cross coupling reaction of
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2,2’-dibromobiphenyls with 1,1-diboronates, 9H-fluorenes were synthesized in
excellent yields.9
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Five-membered cyclic iodonium salts, belong to a class of hypervalent
iodoniums, are particularly interesting because of their stability and numerous
applications in biological studies.10 For example, diphenyleneiodonium chloride
(DPI) has found to be a specific inhibitor for the activity of flavoenzymes.
Whereas, being environmentally benign reactants in organic synthesis, cyclic
dibenziodonium salts have been long-term ignored until recent reports
described the activation of C-I bonds in multi-component cascade reactions.11
In connection with our continued interests in exploring reactivity of hypervalent
iodine reagents for multi-arylations,12 herein we reported palladium catalyzed
double Suzuki-Miyaura coupling reaction by using dibenziodoniums for the
synthesis of ortho-tetraaryls (2, Figure 1).
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Figure 1. Selective examples of ortho-tetraaryl derivatives and two of the possible
disconnections for ortho-tetraphenyls.
Results and Discussion
Our investigation began with an examination of the coupling of cyclic
iodonium salt 1a with phenyl boronic acid 2a in the presence of palladium
catalysts, various inorganic bases and a mixture of acetone/water as a solvent.
Pd(dba)2 was found to be the suitable catalyst, and K3PO4 was the optimal base
to furnish the desired product 3aa in 65% yield after 12 hours (entries 1-6,
Table 1). Afterwards, various solvents were screened in the reaction, and the
use of dichloromethane generated the product in 67% yield at room
temperature. Fortuitously, we found that variations in the amount of K3PO4
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markedly influenced the yield of 3aa, an increased loading of K3PO4 (5 equiv.)
lead to an excellent yield of 84% of 3aa. To our delight, the reaction proceeded
efficiently at a lower catalytic loading of 1 mol% Pd(dba)2 and afforded 3aa in
92% yield (entry 15, Table 1). Notably, under the optimized reaction conditions,
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2,2’-diiodobiphenyl was employed for replacement of iodonium 1a
,
ortho-tetraphenyl 3aa were obtained in a moderate yield of 32%, a large
amount of diphenyls was isolated. The formation of diphenyls was ascribed to
both deiodination of 2,2’-diiodobiphenyls and homocoupling of phenyl boronic
acids (entry 16, Table 1).
Table 1. Screening of reaction conditions for double Suzuki– Miyaura reaction.a
Catalyst, Base
B(OH)2
+
I
Solvent
OTf
2a
1a
3aa
Equiv.
of bases
Entry
Catalyst
Base
Solvent
% yieldc
1b
2b
3b
4
Pd(OAc)2
K3PO4
3.0
Acetone/H2O
Acetone/H2O
Acetone/H2O
Acetone/H2O
Acetone/H2O
Acetone/H2O
THF
43
34
49
65
33
11
43
Pd(BINAP)2Cl2 K3PO4
3.0
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
K3PO4
K3PO4
KOH
3.0
3.0
5
3.0
6
KF
3.0
7
K3PO4
3.0
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Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
3.0
3.0
3.0
3.0
3.0
4.0
5.0
5.0
5.0
toluene
iPrOH
H2O
64
49
36
67
65
78
84
92
32
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15 d
16 f
DCM
DCE
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DCM
DCM
DCM
DCM
aUnless otherwise specified, reaction conditions: 1a (0.2 mmol), 2a (0.44 mmol),
catalyst (10 mol ％), base and 4.4 mL solvent; room temperature, 12 hours. bReaction
c
d
f
time is 5 hours. Isolated yield. Catalyst loading was 1 mol ％. 2,2’-Diiodobiphenyl
was used in place of 1a .
With the optimal conditions established, we subsequently examined the
substrate scope of aryl boronic acids to test the feasibility of preparing a variety
of ortho-tetraaryls. The results were summarized in Table 2. Generally, aryl
boronic acids bearing various substituents of halogens, methoxy, phenyl,
cyano, nitro, trifluoromethyl or methyl groups regardless of their electronic
nature, are well tolerated in the reactions. 4-Methoxyphenylboronic acid (2n
gave 3an in the highest yield of 94%, suggesting electron-donating substituents
in favor of the reaction efficiency (3an vs 3ad 3ae; Table 2).
)
,
3-Nitrophenylboronic acid gave a very low yield of 22% (3am). Furthermore, the
substituents on the ortho-, meta- or para- positions of phenyl ring of boronic
acids were employed. The results suggested that the steric effect on the
reaction yields are depended on the substituent employed. For example,
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4-chlorophenylboronic acid (2i) gave the desired product more efficiently than
2-chlorophenylboronic acid (3ai vs 3ag); however, 2-methylphenylboronic acid
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(2k) afforded the higher yield than 4-methylphenylboronic acid (2j).
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2-Methoxybenzeneboronic acid (2o) afforded 3ao in a moderate yield of 43%.
Disubstituted phenyl boronic acid (2f) furnished 3af in 84% yield.
2-Naphthaleneboronic acid and 4-biphenylboronic acid worked well in this
double coupling reaction, the desired product 3ap was obtained in 92% yield
and 3aq was obtained in 80% yield, respectively. Fortunately, heterocyclic
boronic acids such as 2-furanylboronic acid and 3-thienylboronic acid can
transfer the heterocycles into the desired tetraaryls albeit in a moderate yields
of 27% and 45%, respectively (3ar and 3as, Table 2). However,
4-pyridylboronic acid resulted in no product at all.
Table 2. Scope of diverse aryl boronic acids in Suzuki reactions. a,b
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R
4
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8
Pd(dba)2 (1 mol %)
K3PO4 (5 equiv.)
B(OH)2
DCM, R.T.
12 h
+
I
R
OTf
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R
2
1a
3
Br
F
F3C
NC
CN
3ae, 66
Cl
Br
3ab, 88
F
CF3
3ac, 59
3ad, 62
Cl
Cl
Cl
Cl
3ah, 89
Cl
3ai, 91
3ag, 65
3af, 84
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MeO
OMe
MeO
OMe
3an, 94
3ap, 92
3ao, 43
3aq, 80
N
S
O
O
S
N
3at, 0
3ar, 27
3as,45
aUnless otherwise specified, reaction conditions: 1a (0.2 mmol), 2 (0.44 mmol),
Pd(dba)2 (1 mol ％), K3PO4 (1.0 mmol) in 4.4 mL DCM; room temperature, 12 hours.
bIsolated yield.
Next, we turned our attention to the scope of cyclic dibenziodonium as
coupling partners. As demonstrated in Table 3, a variety of unsymmetrical
cyclic diphenyleneiodoniums were empolyed to assess substitution effect on
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the reactivity. In general, the iodonium salts with various substitutions
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generated the structural diversity of ortho-tetraaryls (3ba-3ja), which
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demonstrated the generality of this double cross coupling reactions.
Surprisingly, when iodonium salts 1h, 1i and 1j were employed in the reaction,
20 mol% palladium catalyst was necessary for an efficient conversion (73%
yield of 3ha, 63% yield of 3ia, 61% yield of 3ja), the standard catalyst loading of
1 mol% Pd(dba)2 only gave less than 10% yield of desired products after a long
reaction time of 24 hours.
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Table 3. Scope of the cyclic dibenziodoniums in Suzuki reactions.a.c
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aUnless otherwise specified, reaction conditions:
Pd(dba)2 (1 mol ), K3PO4 (1.0 mmol) in 4.4 mL DCM; room temperature, 12
hours. bPd(dba)2 (20 mol ). cIsolated yield.
1 (0.2 mmol), 2a (0.44 mmol),
％
％
To explore the reaction scope for potential utility, we wished to produce
tetraphenylene derivatives which are well studied by H. N. C. Wong.13 We then
chose product of 3aj for a further intramolecular dehydrogenative coupling
reaction (Scholl reaction) to test the possibility of preparation of tetraphenylene
of
5
((1), Scheme 1.). Unfortunately, the Scholl reaction gave the coupling
1
according to the H NMR spectra (see the Supporting
product of
4
but not
5
Information).2g Inspired by our recent report on palladium catalyzed double
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Suzuki
reaction
toward
tetraphenylenes,14
we
chose
1a
and
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6
7
8
9
2,2’-biphenyldiboronic acid
expected, tetraphenylene
6
in the direct double Suzuki-Miyaura reaction. As
was obtained in 21% yield under the standard
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conditions ((2), Scheme 1.). Obviously, this method provides an alternative to
prepare specific tetraphenylene derivatives.
Scheme 1. Double coupling reactions towards tetraphenylenes; DDQ =
2,3-dichloro-5,6-dicyano-1,4-benzoquinone.
Conclusion
In summary, we have developed a method of double Suzuki-Miyaura coupling
reaction between cyclic dibenziodonium salts and arylboronic acids in the
presence of palladium catalyst. As such, a wide range of ortho-tetraaryls was
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synthesized in good to excellent yields of 22-94%. It is anticipated that some
useful molecules of PAHs could be produced by this method in the future.
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Experimental Section
General Methods. The cyclic dibenziodoniums were prepared according to the
literature.10, 11c Unless otherwise stated, all reactions were performed under an
atmosphere of air. Commercially available reagents were used without further
purification. 1H and 13C NMR spectra were recorded at 400 MHz spectrometer. 1H and
13C NMR spectra were referenced internally to residual protio-solvent (1H) or solvent
(13C) resonances and are reported relative to tetramethylsilane. Chemical shifts are
reported in ppm from tetramethylsilane. Data are reported as follows: brs = broad
singlet, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet; coupling
constants in Hz. LRMS and HRMS were measured in EI mode, High resolution mass
spectra (HRMS) was measured in a TOF mass spectrometer. Column
chromatography was performed on silica gel (300-400 mesh). Melting points were
determined in open capillaries and are uncorrected.
General Procedure for the synthesis of 3aa-3at
Aryl boronic acid 2 (0.44 mmol, 2.2 eq.), Pd(dba)2 (1.15 mg, 0.002 mmol, 1 mol ％)
were added to a reaction tube. Then 2 mL DCM was added using a syringe. The
reaction mixture was stirred for 15 min, then cyclic dibenziodoniums 1a (85.6 mg, 0.2
mmol, 1.0 eq.) and anhydrous K3PO4 (212.3 mg, 1.0 mmol, 5.0 eq.) in 2.4 mL DCM
were added. The reaction was stirred at room temperature for 12 hours. After the
solvent was removed in vacuo and the residue was purified by silica gel using eluents
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(hexane) to afford the desired products except for 3ae, 3am, 3an, 3ao (using a
mixture eluents of hexane/ ethyl acetate).
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2,2'-Bis(phenyl)biphenyl (3aa).15 The crude product was purified by flash
chromatography (hexane) to obtain 3aa (white solid, 56.3 mg, 92% yield). M. p.:
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1
117-122 ℃. H NMR (400 MHz, CDCl3): δ 7.48-7.41 (m, 2H), 7.41-7.30 (m, 4H),
7.24-7.16 (m, 2H), 7.10 (t, J = 6.8 Hz, 2H), 7.02 (t, J = 7.2 Hz, 4H), 6.64 (d, J = 6.8 Hz,
4H); 13C NMR (100 MHz, CDCl3): δ 141.0, 140.9, 140.0, 131.7, 129.9, 129.3, 127.46,
127.42, 127.1, 125.9; MS (EI): m/z (%) 306 (M+, 100).
2,2'-Bis(4-bromophenyl)biphenyl (3ab).16 The crude product was purified by flash
chromatography (hexane) to obtain 3ab (white solid, 81.7 mg, 88% yield). M. p.:
1
182-184 ℃. H NMR (400 MHz, CDCl3): δ 7.47-7.31 (m, 6H), 7.15-7.06 (m, 6H),
13
6.44-6.37 (m, 4H); C NMR (100 MHz, CDCl3): δ 139.7, 139.6, 139.5, 131.7, 130.7,
130.6, 129.7, 127.9, 127.7, 120.4; MS (EI): m/z (%) 464 (M+, 100), 304 (81), 152 (67),
228 (31).
2,2'-Bis(4-fluorophenyl)biphenyl (3ac). The crude product was purified by flash
chromatography (hexane) to obtain 3ac (white solid, 42.4 mg, 59% yield). M. p.:
164-167 ℃. 1H NMR (400 MHz, CDCl3): δ 7.47-7.42 (m, 2H), 7.39 (td, J = 7.2, 1.2 Hz,
2H), 7.34 (td, J = 7.6, 1.6 Hz, 2H), 7.11 (dd, J = 7.6, 1.2 Hz, 2H), 6.69 (t, J = 8.8 Hz,
4H), 6.55-6.48 (m, 4H); 13C NMR (100 MHz, CDCl3): δ 161.5 (d, J = 244.0 Hz), 139.8,
136.8 (d, J = 3.1 Hz), 131.6, 130.57 (d, J = 8.0 Hz), 129.8, 127.7, 127.4, 114.3 (d, J =
21.0 Hz); HRMS (EI) for C24H16F2: calculated [M]+, 342.1220. Found, 342.1218.
2,2'-Bis(4-trifluoromethylphenyl)biphenyl (3ad). The crude product was purified by
flash chromatography (hexane) to obtain 3ad (white solid, 54.9 mg, 62% yield). M. p.:
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149-153 ℃. 1H NMR (400 MHz, CDCl3): δ 7.56-7.51 (m, 2H), 7.48 (td, J = 7.6, 0.8 Hz,
2H), 7.40 (td, J = 7.2, 1.2 Hz, 2H), 7.21 (d, J = 8.0 Hz, 4H), 7.17-7.12 (m, 2H), 6.58 (d,
J = 8.0 Hz, 4H); 13C NMR (100 MHz, CDCl3): δ 144.2, 139.5, 139.2, 131.9, 129.8,
129.2, 128.3, 128.1, 128.0, 124.4 (q, J = 4.0 Hz), 124.2 (q, J = 271.0 Hz); HRMS (EI)
for C26H16F6: calculated [M]+, 442.1156. Found, 442.1162.
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2,2'-Bis(4-cyanophenyl)biphenyl (3ae). The crude product was purified by flash
chromatography (hexane/ethyl acetate = 20:1) to obtain 3ae (white solid, 47.0 mg,
66% yield). M. p.: 304-308 ℃.1H NMR (400 MHz, CD3COCD3): δ 8.01 (d, J = 8.0 Hz,
3H), 7.73 (d, J = 8.0 Hz, 3H), 7.56-7.51 (m, 4H), 7.49-7.40 (m, 3H), 7.22 (d, J = 7.6 Hz,
1H), 6.73 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz, CD3COCD3): δ 146.6, 140.6, 140.3,
135.9, 133.1, 132.7, 132.2, 131.1, 131.0, 130.0, 129.6, 119.8, 119.7, 114.8, 111.2;
HRMS (EI) for C26H16N2: calculated [M]+, 356.1313. Found, 356.1309.
2,2'-Bis(2,4-dimethylphenyl)biphenyl (3af). The crude product was purified by flash
chromatography (hexane) to obtain 3af (white solid, 60.9 mg, 84% yield). M. p.:
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112-115 ℃. H NMR (400 MHz, CDCl3): δ 7.58-7.15 (m, 6H), 7.10-6.50 (m, 8H),
2.37-2.18 (m, 6H), 1.67 (s, 3H), 1.33 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 141.1,
139.7, 137.5, 135.8, 131.9, 131.1, 130.8, 126.4, 126.3, 125.2, 21.0, 20.2, 19.5; HRMS
(EI) for C28H26: calculated [M]+, 362.2035. Found, 362.2029.
2,2'-Bis(2-chlorophenyl)biphenyl (3ag).17 The crude product was purified by flash
chromatography (hexane) to obtain 3ag (white solid, 48.8 mg, 65% yield). M. p.:
136-139 ℃. 1H NMR (400 MHz, CDCl3): δ 7.62-7.27 (m, 6H), 7.25-6.72 (m, 10H); 13C
NMR (100 MHz, CDCl3): δ 140.2, 137.9, 133.8, 132.1, 131.4, 130.8, 129.6, 128.2,
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127.3, 126.6, 126.1; MS (EI): m/z (%) 303 (100), 151 (66), 374 (M+, 33), 339 (32), 226
(14).
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2,2'-Bis(3-chlorophenyl)biphenyl (3ah). The crude product was purified by flash
chromatography (hexane) to obtain 3ah (white solid, 66.8 mg, 89% yield). M. p.:
97-100 ℃. 1H NMR (400 MHz, CDCl3): δ 7.51-7.47 (m, 2H), 7.43 (td, J = 7.2, 0.8 Hz,
2H), 7.37 (td, J = 7.2, 1.2 Hz, 2H), 7.13 (d, J = 7.6 Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H),
6.91 (t, J = 8.0 Hz, 2H), 6.47 (s, 2H), 6.42 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 142.4, 139.6, 139.4, 133.5, 131.6, 131.5, 129.6, 129.1, 128.5, 127.9, 127.3,
126.1; HRMS (EI) for C24H16Cl2: calculated [M]+, 374.0629. Found, 374.0621.
2,2'-Bis(4-chlorophenyl)biphenyl (3ai). The crude product was purified by flash
chromatography (hexane) to obtain 3ai (white solid, 68.3 mg, 91% yield). M. p.:
161-164 ℃. 1H NMR (400 MHz, CDCl3): δ 7.48-7.43 (m, 2H), 7.41 (t, J = 7.6 Hz, 2H),
7.35 (t, J = 7.2 Hz, 2H), 7.12 (d, J = 7.2 Hz, 2H), 6.97 (d, J = 8.4 Hz, 4H), 6.49 (d, J =
8.4 Hz, 4H); 13C NMR (100 MHz, CDCl3): δ 139.6, 139.2, 132.2, 131.6, 130.4, 129.7,
127.8, 127.7, 127.6; HRMS (EI) for C24H16Cl2: calculated [M]+, 374.0629. Found,
374.0634.
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2,2'-Bis(4-methylphenyl)biphenyl (3aj). The crude product was purified by flash
chromatography (hexane) to obtain 3aj (white solid, 55.5 mg, 83% yield). M. p.:
133-135 ℃. 1H NMR (400 MHz, CDCl3): δ 7.35-7.26 (m, 6H), 7.20-7.14 (m, 2H), 6.82
(d, J = 8.0 Hz, 4H), 6.56 (d, J = 8.0 Hz, 4H), 2.26 (s, 6H); 13C NMR (100 MHz, CDCl3):
δ 140.9, 140.0, 138.1, 135.5, 131.6, 129.9, 129.1, 128.1, 127.3, 126.7, 21.0; HRMS
(EI) for C26H22: calculated [M]+, 334.1722. Found, 334.1721.
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2,2'-Bis(2-methylphenyl)biphenyl (3ak).18 The crude product was purified by flash
chromatography (hexane) to obtain 3ak (white solid, 60.9 mg, 91% yield). M. p.:
115-119 ℃. 1H NMR (400 MHz, CDCl3): δ 7.55-7.20 (m, 7H), 7.15-6.90 (m, 6H), 6.85
(t, J = 7.2 Hz, 2H), 6.76-6.65 (m, 1H), 1.67 (s, 3H), 1.37 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 140.9, 139.8, 136.5, 132.1, 131.9, 131.5, 130.7, 130.4, 126.6, 126.4, 126.3,
124.5, 20.3, 19.7; MS (EI): m/z (%) 334 (M+, 100), 319 (30), 229 (13), 151 (13).
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2,2'-Bis(3-methylphenyl)biphenyl (3al).19 The crude product was purified by flash
chromatography (hexane) to obtain 3al (white solid, 50.8 mg, 76% yield). M. p.:
77-79 ℃. 1H NMR (400 MHz, CDCl3): δ 7.46-7.41 (m, 2H), 7.40-7.27 (m, 4H), 7.15 (dd,
J = 7.6, 1.2 Hz, 2H), 6.91-6.82 (m, 4H), 6.41 (d, J = 6.8 Hz, 2H), 6.35 (s, 2H), 2.13 (s,
13
6H); C NMR (100 MHz, CDCl3): δ 142.4, 141.0, 140.7, 140.1, 136.9, 131.5, 130.0,
129.7, 127.3, 126.9, 126.5, 126.4, 21.4; MS (EI): m/z (%) 334 (M+, 100), 319 (22), 228
(19), 151 (16).
2,2'-Bis(3-nitrophenyl)biphenyl (3am). The crude product was purified by flash
chromatography (hexane/ethyl acetate = 15:1) to obtain 3am (white solid, 17.4 mg,
1
22% yield). M. p.: 194-197 ℃. H NMR (400 MHz, CDCl3): δ 7.96 (ddd, J = 8.4, 2.0,
0.8 Hz, 2H), 7.62-7.57 (m, 2H), 7.54 (td, J = 7.6, 1.2 Hz, 2H), 7.42 (td, J = 7.6, 1.2 Hz,
2H), 7.28 (t, J = 2.0 Hz, 2H), 7.16-7.08 (m, 4H), 6.82 (d, J = 8.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 147.7, 142.1, 139.1, 138.1, 134.9, 131.8, 129.7, 128.9, 128.6,
128.3, 123.9, 121.3; HRMS (EI) for C24H16N2O4: calculated [M]+, 396.1110. Found,
396.1112.
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2,2'-Bis(4-methoxyphenyl)biphenyl (3an).20 The crude product was purified by flash
chromatography (hexane/ethyl acetate = 60:1) to obtain 3an (white solid, 68.9 mg,
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94% yield). M. p.: 135-138 ℃. H NMR (400 MHz, CDCl3): δ 7.39-7.35 (m, 2H),
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7.34-7.28 (m, 4H), 7.17-7.12 (m, 2H), 6.56 (s, 8H), 3.75 (s, 6H); 13C NMR (100 MHz,
CDCl3): δ 157.9, 140.5, 140.0, 133.6, 131.6, 130.2, 129.8, 127.3, 126.7, 112.9, 55.2;
MS (EI): m/z (%) 366 (M+, 100).
2,2'-Bis(2-methoxyphenyl)biphenyl (3ao). The crude product was purified by flash
chromatography (hexane/ethyl acetate=100:1) to obtain 3ao (colorless oil, 31.5 mg,
43% yield). 1H NMR (400 MHz, CDCl3): δ 7.30-7.10 (m, 10H), 6.75-6.55 (m, 6H), 3.42
(s, 6H); 13C NMR (100 MHz, CDCl3): δ 156.3, 141.5, 137.3, 132.0, 131.5, 130.9, 130.4,
128.0, 126.5, 126.4, 120.1, 110.3, 54.8; HRMS (EI) for C26H22O2: calculated [M]+,
366.1620. Found, 366.1623.
2,2'-di(naphthalen-2-yl)-1,1’-biphenyl (3ap). The crude product was purified by
flash chromatography (hexane) to obtain 3ap (white solid, 74.8 mg, 92% yield). m. p.:
151-156 ℃. 1H NMR (400 MHz, CDCl3): δ 7.69 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 7.6 Hz,
2H), 7.45-7.23 (m, 10H), 7.16 (t, J = 7.6 Hz, 4H), 6.73 (s, 2H), 6.63 (d, J = 8.4 Hz, 2H);
13C NMR (100 MHz, CDCl3): δ 141.0, 140.1, 138.5, 133.1, 131.7, 131.6, 130.1, 128.1,
128.0, 127.7, 127.4, 127.3, 127.2, 126.3, 125.5, 125.4; HRMS (EI) for C32H22:
calculated [M]+, 406.1722. Found, 406.1726.
4,4'''-diphenyl-o-quaterphenyl (3aq).21 The crude product was purified by flash
chromatography (hexane) to obtain 3aq (white solid, 73.4 mg, 80% yield). M. p.:
191-193 ℃. 1H NMR (400 MHz, CDCl3): δ 7.57 (d, J = 7.2 Hz, 4H), 7.50 (dd, J = 7.6,
1.2 Hz, 2H), 7.48-7.30 (m, 10H), 7.28-7.18 (m, 6H), 6.67 (d, J = 8.4 Hz, 4H); 13C NMR
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(100 MHz, CDCl3): δ 140.9, 140.5, 140.0, 139.9, 138.6, 131.7, 129.8, 129.5, 128.7,
127.6, 127.3, 127.1, 126.9, 126.1; MS (EI): m/z (%) 458 (M+, 100).
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2,2'-di(furan-2-yl)-1,1’-biphenyl (3ar). The crude product was purified by flash
chromatography (hexane) to obtain 3ar (white solid, 15.5 mg, 27% yield). M. p.:
148-153 ℃. 1H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 8.0 Hz, 2H), 7.48-7.42 (m, 2H),
7.34-7.26 (m, 4H), 7.18 (d, J = 7.6 Hz, 2H), 6.12 (q, J = 1.6 Hz, 2H), 5.36 (d, J = 3.6
Hz, 2H); 13C NMR (100 MHz, CDCl3) δ: 152.1, 141.3, 138.2, 130.4, 129.6, 127.9,
127.4, 126.1, 111.4, 108.5; HRMS (EI) for C20H14O2: calculated [M]+, 286.0994. Found,
286.0993.
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2,2'-di(thiophen-3-yl)-1,1’-biphenyl (3as). The crude product was purified by flash
chromatography (hexane) to obtain 3as (white solid, 28.7 mg, 45% yield). M. p.:
111-113 ℃. 1H NMR (400 MHz, CDCl3): δ 7.40-7.28 (m, 8H), 6.96 (dd, J = 5.2, 3.2 Hz,
2H), 6.51 (dd, J = 2.8, 1.2 Hz, 2H), 6.44 (dd, J = 4.8, 1.2 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 141.5, 140.0, 135.8, 131.1, 129.3, 128.2, 127.6, 127.1, 123.7, 122.3; HRMS
(EI) for C20H14S2: calculated [M]+, 318.0537. Found, 318.0541.
General Procedure for the Synthesis of 3ba−3ja
Phenyl boronic acid 2a (53.6 mg, 0.44 mmol, 2.2 eq.), Pd(dba)2 (1.15 mg, 0.002
mmol, 1 mol ％) were added to a reaction tube. Then 2 mL DCM was added using a
syringe. The reaction mixture was stirred 15 min, then cyclic dibenziodoniums 1 (0.2
mmol, 1.0 eq.) and K3PO4 (212.3 mg, 1.0 mmol, 5.0 eq.) in 2.4 mL DCM were added.
The reaction was stirred at room temperature for 12 hours. After the solvent was
removed in vacuo and the residue was purified by silica gel using eluent (hexane) to
afford the desired products except 3ba-3ja (using a proper mixture of eluents of
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3’,5’-Dimethyl-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3ba). The crude product was purified
by flash chromatography (hexane) to obtain 3ba (white solid, 56.2 mg, 84% yield). M.
p.: 97-99 ℃. 1H NMR (400 MHz, CDCl3): δ 7.29 (d, J = 2.8 Hz, 3H), 7.23-7.17 (m, 1H),
7.14-7.01 (m, 5H), 6.98 (t, J = 6.8 Hz, 2H), 6.85 (s, 1H), 6.67-6.58 (m, 4H), 2.34 (s,
3H), 2.17 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 141.59, 141.28, 141.14, 141.05,
138.2, 136.63, 136.57, 136.49, 132.3, 130.0, 129.8, 129.6, 128.9, 128.4, 127.3, 127.2,
127.0, 126.5, 126.1, 125.7, 21.3, 21.1; HRMS (EI) for C26H22: calculated [M]+,
334.1722. Found, 334.1721.
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4’’-Chloro-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3ca). The crude product was purified by
flash chromatography (hexane) to obtain 3ca (white solid, 47.7 mg, 70% yield). M. p.:
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115-119℃. H NMR (400 MHz, CDCl3): δ 7.39-7.29 (m, 5H), 7.19-7.13 (m, 2H),
7.13-7.06 (m, 2H), 7.01 (q, J = 7.6 Hz, 4H), 6.62-6.55 (m, 4H); 13C NMR (100 MHz,
CDCl3): δ 142.6, 141.0, 140.6, 139.6, 138.7, 138.5, 133.1, 132.9, 131.5, 130.0, 129.8,
129.1, 129.0, 127.7, 127.6, 127.1, 127.0, 126.4, 126.1; HRMS (EI) for C24H17Cl:
calculated [M]+, 340.1019. Found, 340.1016.
4’’-Bromo-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3da). The crude product was purified by
flash chromatography (hexane) to obtain 3da (white solid, 66.3 mg, 86% yield). M. p.:
109-113 ℃. 1H NMR (400 MHz, CDCl3): δ 7.47 (dd, J = 8.0, 2.0 Hz, 1H), 7.38-7.30 (m,
4H), 7.28 (d, J = 8.4 Hz, 1H), 7.20-7.13 (m, 1H), 7.13-7.06 (m, 2H), 7.06-6.96 (m, 4H),
6.59 (td, J = 8.4, 0.8 Hz, 4H); 13C NMR (100 MHz, CDCl3) δ: 142.9, 140.9, 140.6,
139.5, 139.0, 138.7, 133.1, 132.7, 131.5, 130.1, 130.0, 129.1, 129.0, 127.8, 127.58,
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127.56, 127.2, 126.5, 126.1, 121.3; HRMS (EI) for C24H17Br: calculated [M]+,
384.0514. Found, 384.0506.
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4’’-Methoxy-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3ea). The crude product was purified
by flash chromatography (hexane/ethyl acetate = 200:1) to obtain 3ea (white solid,
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59.2 mg, 88% yield). M. p.: 113-119 ℃. H NMR (400 MHz, CDCl3) δ: 7.40-7.36 (m,
1H), 7.36-7.27 (m, 3H), 7.18-7.13 (m, 1H), 7.12-7.05 (m, 2H), 7.01 (q, J = 6.8 Hz, 4H),
6.91 (dd, J = 8.4, 2.4 Hz, 1H), 6.73 (s, 1H), 6.66-6.60 (m, 4H), 3.83 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 158.8, 142.1, 141.1, 140.9, 139.6, 132.7, 132.6, 131.8, 129.9,
129.2, 129.1, 127.4, 127.2, 127.0, 126.0, 125.8, 115.2, 112.6, 55.3; HRMS (EI) for
C25H20O: calculated [M]+, 336.1514. Found, 336.1508.
4’’-Phenyl-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3fa). The crude product was purified by
flash chromatography (hexane) to obtain 3fa (white solid, 66.6 mg, 87% yield). M. p.:
111-114 ℃. 1H NMR (400 MHz, CDCl3): δ 7.70-7.64 (m, 2H), 7.62 (dd, J = 8.0, 2.0 Hz,
1H), 7.52-7.41 (m, 5H), 7.41-7.31 (m, 3H), 7.23-7.17 (m, 1H), 7.15-7.06 (m, 2H),
7.06-6.97 (m, 4H), 6.72-6.63 (m, 4H); 13C NMR (100 MHz, CDCl3): δ 141.4, 141.0,
140.9, 140.6, 140.1, 139.6, 139.1, 132.2, 131.7, 130.0, 129.2, 128.8, 128.7, 127.5,
127.3, 127.1, 127.0, 126.0, 125.9, 125.6; HRMS (EI) for C30H22: calculated [M]+,
382.1722. Found, 382.1718.
2-([1,1’-Biphenyl]-2-yl)-1-phenylnaphthalene (3ga). The crude product was purified
by flash chromatography (hexane) to obtain 3ga (white solid, 27.8 mg, 39% yield). M.
p.: 122-127 ℃. 1H NMR (400 MHz, CDCl3): δ 7.87 (d, J = 8.0 Hz, 1H), 7.81 (d, J = 8.4
Hz, 1H), 7.53 (d, J = 8.8 Hz, 1H), 7.50-7.41 (m, 2H), 7.36-7.20 (m, 5H), 7.20-7.14 (m,
2H), 7.13-6.99 (m, 5H), 6.91 (dd, J = 8.0, 1.6 Hz, 2H), 6.47 (d, J = 7.2 Hz, 1H); 13C
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NMR (100 MHz, CDCl3): δ 141.1, 140.8, 140.1, 138.3, 137.9, 137.8, 132.7, 132.5,
132.1, 131.3, 131.0, 129.9, 129.7, 129.5, 127.8, 127.6, 127.4, 127.22, 127.20, 127.0,
126.6, 126.4, 126.3, 126.2, 125.9, 125.5; HRMS (EI) for C28H20: calculated [M]+,
356.1565. Found, 356.1559.
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4’’-Methyl-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3ha). The crude product was purified by
flash chromatography (hexane) to obtain 3ha (white solid, 46.7 mg, 73% yield). M. p.:
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103-107 ℃. H NMR (400 MHz, CDCl3): δ 7.41-7.36 (m, 1H), 7.36-7.27 (m, 3H),
7.19-7.13 (m, 2H), 7.08 (q, J = 7.2 Hz, 2H), 7.04-6.95 (m, 5H), 6.62 (t, J = 7.2 Hz, 4H),
2.38 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 141.06, 141.01, 140.8, 139.2, 137.05,
136.97, 131.8, 131.5, 130.7, 129.9, 129.20, 129.17, 127.8, 127.39, 127.35, 127.2,
127.0, 125.8, 21.1; HRMS (EI) for C25H20: calculated [M]+, 320.1565. Found,
320.1569.
4’’,5’-Dichloro-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3ia). The crude product was purified
by flash chromatography (hexane) to obtain 3ia (white solid, 47.3 mg, 63% yield). M.
p.: 147-152 ℃. 1H NMR (400 MHz, CDCl3): δ 7.35-7.26 (m, 4H), 7.16 (d, J = 2.0 Hz,
2H), 7.12 (t, J = 7.2 Hz, 2H), 7.03 (t, J = 7.6 Hz, 4H), 6.60-6.53 (m, 4H); 13C NMR (100
MHz, CDCl3): δ 142.6, 139.4, 137.3, 133.5, 132.8, 130.0, 128.9, 127.7, 127.2, 126.6;
HRMS (EI) for C24H16Cl2: calculated [M]+, 374.0629. Found, 374.0634.
4’’-(Trifluoromethyl)-1,1’:2’,1’’:2’’,1’’’-quaterphenyl (3ja). The crude product was
purified by flash chromatography (hexane) to obtain 3ja (white solid, 45.7 mg, 61%
yield). M. p.: 107-112 ℃. 1H NMR (400 MHz, CDCl3): δ 7.60-7.49 (m, 2H), 7.40 (s, 1H),
7.40-7.33 (m, 3H), 7.19-7.14 (m, 1H), 7.10 (q, J = 7.2 Hz, 2H), 7.01 (td, J = 7.6, 3.6 Hz,
4H), 6.57 (t, J = 8.0 Hz, 4H); 13C NMR (100 MHz, CDCl3): δ 143.9, 141.8, 141.1, 140.6,
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139.7, 138.8, 132.2, 131.6, 130.3, 130.0, 129.3, 129.2, 128.2, 127.81, 127.78, 127.4,
127.0 (q, J = 3.1 Hz), 126.8, 126.4, 124.4 (q, J = 271.0 Hz), 123.8 (q, J = 3.5 Hz);
HRMS (EI) for C25H17F3: calculated [M]+, 374.1282. Found, 374.1276.
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General Procedure for the Synthesis of 4.
ortho-Tetraaryl 3aj (66.9 mg, 0.2 mmol, 1.0 eq.), 20 mL DCM (distilled) were added to
a Schlenk tube. Then 1 mL CF3SO3H and DDQ (90.8 mg, 0.4 mmol, 2.0 eq.) were
subsequently added using a syringe at ~0 ℃. The reaction was stirred at 0℃ for 3
hours. After completion of the reaction, it was quenched with a saturated aqueous
solution of NaHCO3 (20 mL). The dichloromethane layer was separated and washed
with water and brine solution, then dried over anhydrous Na2SO4 and filtered. The
solvent was removed in vacuo and the residue was purified by silica gel using a
proper eluent (hexane) to afford the desired product 4 (white solid, 36.6 mg, 55%
1
yield). M. p.: 165-171 ℃. H NMR (400 MHz, CDCl3): δ 8.82 (s, 1H), 8.72-8.58 (m,
3H), 8.55 (d, J = 8.0 Hz, 1H), 8.51 (s, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 8.0 Hz,
2H), 7.67-7.60 (m, 2H), 7.50 (d, J = 8.4 Hz, 1H), 7.36 (d, J = 7.6 Hz, 2H), 2.63 (s, 3H),
2,46 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 139.7, 138.4, 137.3, 136.9, 129.9, 129.82,
129.79, 129.6, 129.3, 128.79, 128.76, 127.7, 127.3, 127.1, 126.8, 126.1, 123.8,
123.29, 123.25, 123.1, 121.4, 21.9, 21.2; HRMS (EI) for C26H20: calculated [M]+,
332.1565. Found, 332.1562.
General Procedure for the Synthesis of 7.22
2,2’-Biphenyldiboronic acid 6 (26.6 mg, 0.11 mmol, 1.1 eq.), Pd(dba)2 (5.75 mg, 0.01
mmol, 10 mol ％), cyclic dibenziodoniums 1a (42.8 mg, 0.1 mmol, 1.0 eq.), K3PO4
(106.1 mg, 0.5 mmol, 5.0 eq) in 4 mL DCM were added to a Schlenk tube under
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argon. The reaction was stirred at room temperature for 12 hours. After the solvent
was removed in vacuo and the residue was purified by silica gel using eluent (hexane)
to afford the desired products 7 (white solid, 6.4 mg, 21% yield). M. p.: 233-237 ℃. 1H
NMR (400 MHz, CDCl3): δ 7.31-7.26 (m, 8H), 7.20-7.12 (m, 8H); 13C NMR (100 MHz,
CDCl3): δ 141.5, 129.0, 127.2; MS (EI): m/z (%) 304 (M+, 100).
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Acknowledgements
This work was supported by grants from the National Nature Science
Foundation of China (NSFC Nos. 21472213, 21202186), as well as by
Croucher Foundation (Hong Kong) in the form of a CAS-Croucher Foundation
Joint Laboratory Grant and the Innovation Program of Shanghai Municipal
Education Commission (No. 14YZ144). This research program was under the
auspices of Professor Henry N.C. Wong, whom we thank for helpful
discussions and generous support.
Supporting Information
The copies of 1H, 13C NMR spectra for all products. The Supporting Information is
available free of charge via the internet at http://pubs.acs.org.
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