Direct Aryl-Aryl Coupling without Pre-Functionalization Enabled by Excessive Oxidation of Two-Electron Ag(I)/Ag(III) Catalyst

Article abstract of DOI:10.1002/adsc.201800213

Reported herein is a catalytic platform for formation of unsymmetrical biaryls by the coupling between inert Csp²?CH₃ and Csp²?H via a tandem catalytic strategy. The platform utilizes traditional AgNO₃ catalyst and excess amount of K₂S₂O₈ oxidant. The excessive oxidant present converts the traditional one-electron Ag(I)/Ag(II) chemistry to two-electron Ag(I)/Ag(III) one, enabling one-pot synthesis of aryl-aryl scaffolds by using unactivated cheap commodity chemicals. (Figure presented.).

Full text of DOI:10.1002/adsc.201800213

Title: Direct aryl-aryl coupling without pre-functionalization enabled by
excessive oxidation of two-electron Ag(I)/Ag(III) catalyst
Authors: Ajay Singh, Min-Gyu Kim, Hyune-Jea Lee, Rakhi Singh,
Seung Hwan Cho, and Dong-Pyo Kim
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800213
Link to VoR: http://dx.doi.org/10.1002/adsc.201800213

Advanced Synthesis & Catalysis
10.1002/adsc.201800213
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Direct aryl-aryl coupling without pre-functionalization enabled by
excessive oxidation of two-electron Ag(I)/Ag(III) catalyst
a,b
c
a
a
d
Ajay K. Singh, Min-Gyu Kim, Hyune-Jea Lee, Rakhi Singh, Seung Hwan Cho,
a
Dong Pyo Kim *
aCenter for Intelligent Microprocess of Pharmaceutical Synthesis, Department of Chemical Engineering, POSTECH
(
Pohang University of Science and Technology), Pohang 376-73, Korea.
b
Division of Organic Synthesis and Process Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad, India.
c
Beamline Research Division, Pohang Accelerator Laboratory (PAL), POSTECH (Pohang University of Science and
Technology), Pohang 376-73, Korea.
d
Department of Chemistry, POSTECH (Pohang University of Science and Technology), Pohang 376-73, Korea.
Email: dpkim@postech.ac.kr (D. -P. Kim).
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. Reported herein is a catalytic platform for
Keywords: C-C coupling; commodity chemical;
Ag(I)/Ag(III); radical mechanism; in-situ XAS
formation of unsymmetrical biaryls by the coupling between
2
2
inert Csp -CH
The platform utilizes traditional AgNO
amount of K oxidant. The excessive oxidant present
3
and Csp -H via a tandem catalytic strategy.
3
catalyst and excess
2 2 8
S O
converts the traditional one-electron Ag(I)/Ag(II) chemistry
to two-electron Ag(I)/Ag(III) one, enabling one-pot
synthesis of aryl-aryl scaffolds by using unactivated cheap
commodity chemicals.
Introduction
2
2
H/Csp –H or Csp2–
3
CO
CO
2
2
H/Csp –H bonds, Csp –CO
2
2
[4g, 6]
During the past decades, transition-metal-catalyzed cross-
couplings have become one of the most powerful tools to
form biaryls,[1] which are prevalent structural motifs found
in electronic materials and biologically active
compounds.[ But, the methods typically require pre-
activated electrophiles to react with organometallic
nucleophiles. Consequently, direct C-H coupling reactions
of simple arenes with prefunctionalized arenes have been
pursued recently because this direct approach allows
extremely efficient manipulation of substrates without the
requirement of prefunctionalization.[3] There are various
reports that secondary commodity arenes (-I, -Cl, -Br, -
H/Csp –H to extend the decarboxylative approach.
However, these synthetic approaches suffer from laborious
multi-step synthesis of carboxylic acid substrates. To the
best of our knowledge there is only one report where
primary commodity chemicals (benzyl alcohol and
styrene) is appropriated as a cross coupling partner with
2]
suitable arenes.[7]
However, this methodology is
associated with several drawbacks such as high reaction
temperature, low yield, less availability and high price of
primary commodity chemical.[8]
Therefore, the development of new reaction routes,
which overcome these shortcomings would be highly
B(OR)
2
, -COOH, -OR, -COOR, -N
2
X etc) directly cross-
desirable. It is highly desirable for the purpose to use the
2
3
[3h, 4]
2
coupled with Csp -H or Csp -H bond of arenes.
In
inert methylbenzene (Csp -CH
3
) for developing more
particular, Ag-catalyzed decarboxylative addition of alkyl
or aryl centered radical to (hetero)arenes (Minisci reaction)
is one of well-known method for the formation of C-C
bonds using inexpensive substrates in the absence of base
and byproducts under facile reaction conditions.[5]
Thereafter, many researchers have utilized/modified
efficient and selective radical-mediated C-C coupling in a
one-pot and tandem catalytic manner. Recently, a concept
of ‘tandem catalysis’, where a single or a combination of
catalysts could bring about mechanistically distinct (or
fundamentally different) reactions in a single vessel, has
received much attention for multi-step organic synthesis.[
In particular, auto-tandem catalysis, unlike orthogonal- or
9]
3
3
3
2
diverse pairs of Csp –CO H/Csp –H bonds, Csp –
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
assisted-tandem catalysis, allows a single catalyst to
promote without any chemical triggers more than two
chemical transformations that follow entirely different
reaction mechanisms. In general, an one-pot tandem
catalytic process minimizes additional workup or column
chromatographic purification/separation of intermediates
the oxidant, no observable product yield was attained with
2 2 8 2 2 2
oxidants other than K S O such as TBHP, H O and O .
Table 1. Evaluation of reaction conditions.a
,
associated with multi-step reactions and complementarily
[
10]
maximizes time-, energy- and material-efficiency. Here,
we report a successful one-pot, tandem Ag-catalytic
strategy for direct conversion of commodity chemicals into
aryl-aryl scaffolds in a single step (Scheme 1). Here, we
report a successful one-pot, tandem Ag-catalytic strategy
for direct conversion of commodity chemicals into aryl-
aryl scaffolds in a single step (Scheme 1).
Entry
R
[Ag] cat.
oxidant
Yield
%)[b]
84 (80)
73
(
[c]
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
H
H
H
H
H
H
H
H
F
AgNO
3
K
K
K
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
2
2
2
S O
2 8
S O
2 8
S O
2 8
S O
2 8
S O
2 8
S O
2 8
S O
2 8
S O
2 8
S O
2 8
S O
2 8
S O
2 8
AgOAc
AgCl
AgTFA
<1
57
66
31
7
55
43
82
<1
<1
<1
<1
78
AgBF
Ag
AgCN
Ag SO
4
2
O
2
4
AgTFA
AgO
1
1
0
1[
d]
AgNO
AgNO
AgNO
AgNO
AgNO
3
3
3
3
3
1
1
1
1
2
3
4
5
TBHP
H
2
O
2
O
2
K
2
S O
2 8
[
a] Reaction conditions: substitutedmethylbenzene (1, 0.25
mmol), anhydrous benzene (2, 10 mmol), CH
3
CN (1 mL),
o
K
2
S
2
O
8
(2.0 mol), AgX (35 mol %) for 20 h at 120 C. [b]
Yield are determined by GC analysis with internal standard
dodecane, at least three measurements were taken to obtain
an average yield. [c] Yield in parenthesis indicated isolated
yield. [d] Runs the reaction without 1.
Scheme 1. The direct oxidative arylation of aromatic C–H
bonds via the synergistic merger of transition metal
catalyst and oxidant.
With optimization result in our hand, we moved to
evaluate a wide variety of substrates with respect to
various methylbenzene derivatives. As shown in Scheme 2,
various ortho-, meta-, para-substituted, as well as di-
substituted commodity chemicals provided the desired
cross-coupling products in good to excellent yields (57-
Results and Discussion
Tandem catalytic approach was initially attempted for
methylbenzene (CSP2-CH
3
) as a starting material with
benzene (CSP2-H) in the presence of silver catalyst and
9
1%). The reaction tolerated a variety of electron-
withdrawing substituents such as fluoro (3b, 3k), chloro
3c, 3l), bromo (3d, 3m, 3p), iodo (3e, 3n), nitrile (3h),
excess amount of potassium persulfate as an oxidant at 120
oC. Gratifyingly, when silver nitrate was employed as a
(
3
catalyst in CH CN as a solvent, the desired biphenyl
nitro (3g), ester (3i), biphenyl (3j), polycyclic (3r), as well
as electron. The direct coupling reactions of
methylbenzenes (1) with substituted arenes (4) was next
examined. Upon reacting with arenes having electron-
withdrawing substituents such as chloro (5a), bromo (5b),
nitro (5c), even with weakly activating phenyl
product 3 was formed in 84% GC yield (Table 1, entry 1).
The employment of other silver salts as a catalyst (entries
2
-9) showed low reactivity compared to silver nitrate.
Notably, the high valent silver (II) oxide (AgO, preferably
Ag(II)) exhibited 82% yield (entry 10), similar to the yield
provided by the AgNO catalyst. However, AgNO is
3 3
preferable owing to low cost and abundant availability.
Note that the biaryl product 3 was not formed without
employing 1 under the reaction conditions. With regard to
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
Scheme 3. Direct arylation of methylbenzenes with
various substituted arenes. Reaction conditions:
methylarene (1, 0.25 mmol), K
2 2 8 3
S O (2.0 mmol), AgNO
(
35 mol%), CH CN (1 mL), arene (4) (10 mmol) for 20 h,
3
Yields are those of isolated products and the relative ratio
of regioisomer was calculated using GC-MS.
Mechanistic
decarboxylative coupling are rare.
studies
on
the
4g, 12]
silver-catalyzed
In this work, we
[
utilize Ag K-edge X-ray absorption near edge structure
(
(
XANES) and extended X-ray absorption fine structure
EXAFS) analyses for an insight. Oxidation states of both
catalysts and their intermediates, and local structural
environment around Ag cation in various reaction mixtures
are investigated at different steps. The signature peak
Scheme. 2 Direct arylation of methylarenes with benzene.
Reaction conditions: (a) methylarene (0.25 mmol),
benzene (10 mmol), K
mol%), CH CN (1 mL) at 120 °C for 20 h; [b]
Dimethylarene (0.0125 mmol), benzene (10 mmol),
(2.0 mmol), AgNO (35 mol%) CH CN (1 mL) at
20 °C for 20 h; Yields refer to isolated yields.
2 2 8 3
S O (2.0 mmol), AgNO (35
3
feature of the XANES spectra of pristine AgNO was
+
10
0
3
confirmed first for Ag species ([Kr]4d 5s ), originating
from the dipole-allowed transition of 1s electron to
unoccupied 5p orbital (Figure 1A).[13] In the case of
K
1
2 2
S O
8
3
3
3 2 2 8
simple mixture of AgNO and K S O , the Ag oxidation
state was effectively changed from Ag(I) state to a mixed
group (5d) (Scheme 3), various arylation products were
obtained by a single step reaction with excellent to good
yields ranging from 77 to 87% as inseparable
regioisomeric mixtures. Unfortunately, no reaction took
place when pyridine was employed as a coupling partner.[8]
Ag(II) oxidation state. When the reaction solution
o
(
methylbenzene and benzene) was heated at 120 C in the
3 2 2 8
presence of AgNO and excess amount of K S O oxidant,
however, it was oxidized to form Ag (III) state (Figure
A).[14] An interpretation for the oxidation state is that the
1
o
fast reaction kinetics of methylbenzene at 120 C rapidly
•-
consumed SO
4
for performing serial oxidative coupling
by forming a stable but abnormal Ag(III) catalyst
intermediate throughout the reaction. The radial
distribution functions (RDF) of Fourier-transformed (FT)
Ag K-edge EXAFS spectra in Figure 1B show that the
pristine catalyst has intense singlet peaks at around 2.0 Å
Scheme. 4 One-step intramolecular coupling reaction.
Fused ring compounds are mostly utilized for anti-
malarial, antiviral activity.[11] Therefore, we turned our
attention to utilizing 2-methylbenzophenone (6) as a
substrate in an intramolecular C-C bond formation. The
reaction of 6 efficiently produced the corresponding 9H-
fluoren-9-one (7) in 51% isolated yield under the
optimized reactions, as shown in Scheme 4, which further
extends the applicability of the developed protocol.
(
non-phase shift corrected), corresponding to the Ag-O in
nitrate for (Figure 1B). The Ag-O bond length, however,
was reduced to 1.85 Å for the simple mixture of AgNO
and K , and further shortened to 1.83 Å upon heating
the reaction solution mixtures (methylbenzene, benzene,
3
2 2 8
S O
acetonitrile, K
These results indicate that the NO
2
S
2
O
8
and AgNO
3
), as seen in Figure 1B.
-
3
was gradually replaced
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
with sulphate via two-electron oxidative process by
forming the catalyst intermediate Ag(I)/Ag(III) structure,
which was confirmed by investigating the EXAFS and
XANES of reference Ag compounds with different degrees
of covalent and ionic bond character.13 This two-electron
oxidative transfer Ag(I)/Ag(III) system for generation of
SO4•- is different from one-electron redox chemistry
(Ag(I)/Ag(II)) as generally reported, which provides a new
mechanistic insight into the Minisci type reactions.[
4g, 12]
Figure 1. X-ray absorption spectroscopy of tandem silver catalyzed oxidative arylation reaction: (A) Ag-K edge XANES;
(
(
(
B) XAFS radial distribution functions of Fourier-transformed spectra for various cases; P (Pristine catalyst AgNO
3
); M1
(2 mmol), methylbenzene
(2 mmol), methylbenzene (0.25 mmol), anhydrous benzene (10
(2 mmol), methylbenzene (0.25 mmol), anhydrous benzene (10 mmol),
mixture of AgNO
3
(35 mol%), K
2
S
2
O
8
(2 mmol)); M2 (mixture of AgNO
3 2 2 8
(35 mol%); K S O
0.25 mmol)); M3 (mixture of AgNO
3
(35 mol %); K
2 2 8
S O
mmol)); M4 (mixture of AgNO
CH CN (1 mL)); CR1, CR2, CR3, CR4 (mixture of AgNO
anhydrous benzene (10 mmol), CH
3
(35 mol %); K
2
S
2
O
8
3
3
(35 mol %); K
CN (1 mL)) heating at 120 C for 1, 6, 16, 20 h respectively.
2
S
2
O
8
(2 mmol), methylbenzene (0.25 mmol),
o
3
Figure 2. Proposed evolution of local structure around silver catalyst with help of reference structure of Ag cation.
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
Figure 3. GC Spectrum of crude reaction mixture from methylbenzene coupling (A) Solution; (B) gas product Reactant
o
methylbenzene (0.25 mmol); benzene (10.0 mmol); MeCN (1mL); catalyst AgNO
for time 6 h.
3
(35 mol%); K
2
S
2
O
8
(2.0 mmol); at 120 C
Based on previous reports regarding the local structure of which led to a very low yield (~7%) of the cross-coupled
[
14-15] [15-16]
and our experimental evidence, a product.[8] Furthermore, the presence of radical scavengers
silver oxide,
plausible silver intermediate structure (tetrahedron (Td) to such as tetramethylpiperidine N-oxide TEMPO) and tert-
square planner (D4h)) is depicted in Figure 2.The insight butyl-4-methylphenol (BHT) under identical reaction
[
8]
gained so far can be utilized to propose detailed reaction conditions did not yield any desired arylation product. The
pathways Figure 5, step I. The generation of SO •
-
species is reaction proceeds further to form benzoic acid (C) and
4
detailed in step I of Figure 5. The sulfate ion radical thus consecutive decarboxylation is followed by generation of
formed acts on methylbenzene (1) to generate an unstable aryl free radical. GC-MS detection (Figure 3B) of the
benzyl radical in step II of Figure 5. It then forms a stable gaseous sample from the decarboxylation process revealed
•-, which the generation CO
benzyl hydrogen sulfate (A) by reaction with SO . Finally, the coupling between the aryl
4 2
was observed from GC measurement of the 6 h reaction radical (D) and (benzene produces the desired arylated
mixture shown in Figure 3A. Subsequently, the continuity of product through the oxidation of cyclohexadienyl radical
the reaction leads to formation of benzaldehyde (B) (Figure intermediate by SO
), as detected unequivocally in the earlier stage of the effect were seen in both parallel reactions and competitive
4
•-. Next, lower rates of kinetic isotope
4
reaction confirm that a free radical redox reaction pathway reactions, reperenting that C−H bond cleavage is not
involving SO •
-
is indeed being followed, we replaced involved in the rate-limiting step (Scheme 5). Based on
a typical radical initiator, tert-butyl previous reports and our experimental pieces of evidence a
4
K
2
S
2
O
8
with
hydroperoxide (TBHP), without changing the other reaction plausible reaction mechanism is depicted in Figure 5.
5
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
Scheme 5. Kinetic Isotope effect.
Conclusion
The presence of the oxidant K
2
S
2
O
8
in excess of the usual
amount for the traditional AgNO
3
catalyst system alters the
usual Ag(I)/Ag(II) chemistry to unexpected Ag(I)/Ag(III)
chemistry, thereby allowing one-step direct arylation of
commodity chemicals. The scope of the direct aryl-aryl
coupling
includes
coupling
groups
of
various
Figure 4. Time profile for oxidative arylation reaction of
methylbenzene reagent. Methylbenzene (0.25 mmol);
methylbenzene derivatives, in addition to coupling to fused
ring product and formation of hexaarylbenzene. These facile
arylations of commodity chemicals could become a
powerful synthetic tool for variouskinds of demethylation-
initiated bond formations (e.g. C-C, C-F (Cl), C-N, C-Si),
which is highly useful for the production of value added
chemicals such as natural products and chemicals,
particularly in the pharmaceutical and agrochemical
industries.
benzene (10 mmol); MeCN (1mL); catalyst AgNO
3
(35
o
mol%); K
2
2
S O
8
(2.0 mmol) at 120 C; time varied; yields
are determined by GC analysis with internal standard
dodecane, at least three measurements were taken to obtain
an average yield.
Figure 5. Proposed reaction pathways for the tandem silver catalyzed oxidative arylation reaction: two types of catalyst
intermediates, Ag(I)/Ag(III) & Ag(III) states, are shown with the dotted line indicating new bond generation during the
reaction, proposed by XANES and EXAFS analyses.
syringe. Then the tube was sealed by a Teflon screwcap and
sonicated for 5 min and placed in an oil bath at 120 C as
pre-heated. After reaction for 20 h, the mixture was filtered
through a short plug of silica gel and washed with DCM (20
Experimental Section
o
General procedure for direct coupling of benzene with
methylbenzene:
To an oven-dried 4 mL Ace pressure tubes equipped with a mL). 2M sodium hydroxide (2 mL) was added. The aqueous
Teflon coated magnetic stirbar, K
AgNO
(35 mol%), methylbenzene (1, 0.25 mmol) were washed with water (30 mL) then washed with brine (30 mL).
added. Then benzene (10 mmol) or substituted arenes (5.0 The organic phase was dried over Na SO and concentrated
2 2 8
S O
(2 mmol, 405.6 mg), layer was extracted with dichloromethane (3 X 20 mL),
3
2
4
mmol, if liquid) and MeCN (1.0 mL) were added using a under reduced pressure. The product was purified using
6
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
flash column chromatography on 200–300-mesh silica gel
(3e) 4‐ Iodobiphenyl
with hexane/ethyl acetate as an eluent.
The title compound was prepared according to the general
procedure as described above using benzene (10 mmol) and
(
3a) 1,1'-Biphenyl
4
-iodotoluene (0.25 mmol) as substrates. The crude mixture
The title compound was prepared according to the general
procedure as described above using benzene (10 mmol) and
methylbenzene (0.25 mmol) as substrates. The crude
mixture was purified by flash column chromatography
was purified by flash column chromatography (hexane/ethyl
acetate, 95:5) to give the product 3e (56.0 mg, 80%). H
1
NMR (400 MHz, CDCl
3
):  7.30-7.37 (m, 2H), 7.34 – 7.44
(
(
m, 3H), 7.52 – 7.54 (m, 2H), 7.73-7.76 (m, 2H), 13C NMR
(
hexane/ethyl acetate; 95:5) to give the product 3a (30.8 mg,
CDCl
3
, 150 MHz): 93.0, 126.9, 127.70, 128.91, 129.02,
1
8
7
1
0%). H NMR (300 MHz, CDCl
.70-7.74 (m, 4H), 7.89‐ 7.92 (m, 4H). C NMR (CDCl
3
): 7.61‐ 7.65 (m, 2H),
+
1
37.85, 140.08, 140.753. MS (EI): found: 280 (M ).The
1
3
3
,
1
observed characterization data ( H) was consistent with the
previous report in the literature.[18]
50 MHz): 127.50, 127.60, 129.12, 141.56. MS (EI):
+
1
found: 154 (M ). The observed characterization data ( H)
was consistent with the previous report in the literature.[16]
(3f) 4‐ Methoxybiphenyl
(
3b) 4‐ Fluorobiphenyl
The title compound was prepared according to the general
procedure as described above using benzene (10 mmol) and
The title compound was prepared according to the general
procedure as described above using benzene (10 mmol) and
4
mixture was purified by flash column chromatography
(
1
-methoxy-4-methylbenzene (0.25 mmol) as substrates. The
crude mixture was purified by flash column chromatography
-fluorotoluene (0.25 mmol) as substrates. The crude
(
hexane/ethyl acetate, 95:5) to give the product 3f (22.5 mg,
1
4
6
7
1
(
(
9%). H NMR (300 MHz, CDCl
3
):  3.84 (s, 3H), 6.95-
hexane/ethyl acetate, 95:5) to give the product 3b (32.3 mg,
.98 (m, 2H), 7.28‐ 7.31 (m, 1H), 7.39-7.42 (m, 2H), 7.51-
1
7
3
5%). H NMR (300 MHz, CDCl
3
):  7.09-7.15 (m, 2H), 7.
13
.55 (m, 4H). C NMR (CDCl , 150 MHz):  55.37, 114.21,
3
13
2– 7.36 (m, 1H), 7.41-7.46 (m, 2H), 7.52-7.60 (m, 4H). C
):  115.52 (d, J = 21.2 Hz), 127.0,
27.27, 128.66 (d, J = 8.0 Hz), 128.83, 137.37 (d, J = 7.1
Hz), 140.28, 161.26 (d, J = 244.2 Hz). MS (EI): MS (EI):
26.67, 126.76, 128.17, 128.73, 133.80, 140.85, 159.16. MS
NMR (150 MHz, CDCl
1
3
+
EI): found: 184 (M ). The observed characterization data
1
H) was consistent with the previous report in the
[
16]
literature.
+
1
found: 172 (M ). The observed characterization data ( H)
was consistent with that previously reported in the
literature.[16]
(3g) 4‐ Nitrobiphenyl
The title compound was prepared according to the general
procedure as described above using benzene (10 mmol) and
(
3c) 4‐ Chlorobiphenyl
1
-methyl-4-nitrobenzene (0.25 mmol) as substrates. The
The title compound was prepared according to the general
procedure as described aboveusing benzene (10 mmol) and
crude mixture was purified by flash column chromatography
(
hexane/ethyl acetate, 90:10) to give the product 3g (40.8
4
-chlorotoluene (0.25 mmol) as substrates. The crude
1
mg, 82%). H NMR (300 MHz, CDCl
3
):  7.42 – 7.51 (m,
mixture was purified by flash column chromatography
3
H), 7.61 – 7.62 (m, 2H), 7.72 – 7.74 (m, 2H), 8.28 – 8.30
m, 2H). 13C NMR (CDCl
, 150 MHz): 123.09, 126.37,
26.78, 127.89, 128.13, 137.76, 146.07, 146.62. MS (EI):
(
hexane/ethyl acetate, 95:5) to give the product 3c (36.7 mg,
(
1
3
1
7
7
1
(
(
8%). H NMR (400 MHz, CDCl
.50‐ 7.56 (m, 4H). 13C NMR (75 MHz, CDCl
3
): 7.33‐ 7.46 (m, 5H),
):  127.01,
3
+
1
found: 199 (M ).The observed characterization data ( H)
was consistent with the previous report in the literature.[19]
27.61, 128.42, 128.91, 128.93, 133.40, 139.69, 140.0, MS
+
EI): found: 188 (M ). The observed characterization data
1
H) was consistent with the previous report in the
(3h) 4‐ carbonitrilebiphenyl
literature.[
17]
The title compound was prepared according to the general
procedure as described above using benzene (10 mmmol)
and 4-methylbenzonitrile (0.25 mmol) as substrates. The
crude mixture was purified by flash column chromatography
(
3d) 4‐ Bromobiphenyl
The title compound was prepared according to the general
procedure as described above using benzene (1.0 mL) and 4-
bromotoluene (0.25 mmol) as substrates. The crude mixture
was purified by flash column chromatography (hexane/ethyl
(
hexane/ethyl acetate, 95:5) to give the product 3h (22.4 mg,
1
5
7
0%). H NMR (300 MHz, CDCl
3
): 7.39 – 7.51 (m, 3H),
.56-7.60 (m, 2H), 7.66 – 7.73 (m, 4H). 13C NMR (150
1
acetate, 95:5) to give the product 3d (46.6 mg, 80%). H
MHz, CDCl
1
3
):  110.93, 118.93, 127.23, 127.73, 128.66,
NMR (300 MHz, CDCl
7
3
): 7.33 – 7.37 (m, 1H), 7.41 –
, 150
+
29.11, 132.59, 139.18, 145.68. MS (EI): found: 179 (M ).
.46 (m, 4H), 7.53‐ 7.57 (m, 4H). 13C NMR (CDCl
3
1
The observed characterization data ( H) was consistent with
the previous report in the literature.[17]
MHz): 121.50, 126.91, 127.61, 128.71, 128.87, 131.83,
+
1
39.98, 140.11. MS (EI): found: 233 (M ). The observed
1
characterization data ( H) was consistent with the previous (3i) Methoxymethyl biphenyl-4-carboxylate
report in the literature.[7]
7
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
The title compound was prepared according to the general The title compound was prepared according to the general
procedure as described above using benzene (10 mmol) and procedure as described above using benzene (10 mmol) and
methoxymethyl 4-methylbenzoate (0.25 mmol) as substrates. 1-bromo-2-methylbenzene (0.25 mmol) as substrates. The
The crude mixture was purified by flash column crude mixture was purified by flash column chromatography
chromatography (hexane/ethyl acetate, 95:5) to give the (hexane/ethyl acetate, 95:5) to give the product 3m (41 mg,
1
1
product 3i (42.4mg, 70%). H NMR (CDCl
3
, 400 MHz) 71%). H NMR (400 MHz, CDCl ):  7.18‐ 7.24 (m, 1H),
3

4

1
3.47 (s, 3H), 5.4 (s, 2H), 7.29-7.39 (m, 3H), 7.70-7.72 (m, 7.32‐ 7.46 (m, 7H), 7.65-7.68 (m, 1H). 13C NMR (CDCl
3
,
1
3
H), 8.04-8.07 (m, 2H), C NMR (CDCl
3
, 600 MHz) 150 MHz): 122.64,127.36, 127.59, 127.96, 128.71, 129.38,
+
57.77, 91.00, 127.14, 127.30, 128.23, 128.58, 128.96, 131.28, 133.11, 141.12, 142.61. MS (EI): found: 231 (M ).
30.32, 139.95, 146.05, 165.97. MS (EI): found: 242 The observed characterization data ( H) was consistent with
M ).The observed characterization data ( H) was consistent the previous report in the literature.[7]
1
+
1
(
[
20]
with the previous report in the literature.
(
3n) 2-Iodobiphenyl
(
3j) 1, 1':4, 1''-Terphenyl
The title compound was prepared according to the general
The title compound was prepared according to the general procedure as described above using benzene (10 mmol) and
procedure as described above using benzene (10 mmol) and 1-iodo-2-methylbenzene (0.25 mmol) as substrates. The
4
-methyl-1,1'-biphenyl (0.25 mmol) as substrates. The crude crude mixture was purified by flash column chromatography
mixture was purified by flash column chromatography (hexane/ethyl acetate, 95:5) to give the product 3n (47.0 mg,
1
(
hexane/ethyl acetate, 95:5) to give the product 3j (52.3 mg, 67%). H NMR (400 MHz, CDCl ): 7.01‐ 7.05 (m, 1H),
3
1
13
9
7
1%). H NMR (300 MHz, CDCl
3
):  7.33‐ 7.37 (m, 2H), 7.29‐ 7.48 (m, 7H), 7.96 (dd, J = 6.8 Hz, 1.1 Hz, 1H).
.43‐ 7.48 (m, 4H), 7.62‐ 7.68 (m, 8H). 13C NMR (75 MHz, NMR (CDCl , 150 MHz): 98.63, 127.65, 127.96, 128.13,
C
3
CDCl ): 127.09, 127.38, 127.54, 128.86, 140.16, 140.74. 128.79, 129.28, 130.08, 139.50, 144.22, 146.65. MS (EI):
3
+
+
1
MS (EI): found: 230 (M ). The observed characterization found: 280 (M ).The observed characterization data ( H)
data ( H) was consistent with the previous report in the was consistent with the previous report in the literature.[22]
literature.[16]
1
(
3o) 1, 1':2, 1''-Terphenyl
(
3k) 2-Fluorobiphenyl
The title compound was prepared according to the general
The title compound was prepared according to the general procedure as described above using benzene (10 mmol) and
procedure as described above using benzene (10 mmol) and 2-methyl-1,1'-biphenyl (0.25 mmol) as substrates. The crude
1
-fluoro-2-methylbenzene (0.25 mmol) as substrates. The mixture was purified by flash column chromatography
crude mixture was purified by flash column chromatography (hexane/ethyl acetate, 95:5) to give the product 3o (48.3 mg,
1
(
hexane/ethyl acetate, 95:5) to give the product 3k (31.1 mg, 84%). H NMR (300 MHz, CDCl ): 7.18‐ 7.28 (m, 10H),
3
1
13
7
7%). H NMR (300 MHz, CDCl
3
):  7.12‐ 7.22 (m, 2H), 7.45‐ 7.49 (m, 4H). C NMR (CDCl , 150 MHz): 126.46,
3
7
.27‐ 7.36 (m, 2H), 7.40‐ 7.45 (m, 3H), 7.53‐ 7.56 (m, 2H). 127.48, 127.87, 129.92, 130.62, 140.61, 141.55. MS (EI):
13C NMR (CDCl
, 150 MHz): 116.0 (d, J = 22.9 Hz), found: 230 (M ). The observed characterization data ( H)
+
1
3
1
1
24.40 (d, J = 3.1 Hz), 127.73, 128.51, 129.00, 129.11, was consistent with the previous report in the literature.[23]
29.13 (d, J = 1.9 Hz), 130.84 (J = 3.4 Hz), 135.91, 159.04
(
3p) 3-Bromobiphenyl
+
(
d, J = 246.1 Hz), MS (EI): found: 172 (M ). The observed
1
characterization data ( H) was consistent with the previous The title compound was prepared according to the general
report in the literature.[21]
3l) 2-Chlorobiphenyl
procedure as described above using benzene (10 mmol) and
-bromo-3-methylbenzene (0.25 mmol) as substrates. The
crude mixture was purified by flash column chromatography
1
(
The title compound was prepared according to the general (hexane/ethyl acetate, 95:5) to give the product 3p (46.6 mg,
1
procedure as described above using benzene (10 mmol) and 80%). H NMR (400 MHz, CDCl ): 7.27 (t, J = 6.8 Hz,
3
1
-chloro-2-methylbenzene (0.25 mmol) as substrates. The 1H), 7.34-7.38 (m, 1H), 7.41 – 7.55 (m, 6H), 7.73 (t, J = 2.0
Hz, 1H). 13C NMR (CDCl
27.16, 127.91, 128.80, 128.93, 130.19, 130.22, 130.26,
, 150 MHz): 122.93, 125.8,
crude mixture was purified by flash column chromatography
3
(
hexane/ethyl acetate, 95:5) to give the product 3l (35.8 mg,
1
1
+
7
7
6%). H NMR (300 MHz, CDCl
3
): 7.27‐ 7.35 (m, 3H), 130.30, 139.76, 143.40. MS (EI): found: 232 (M ). The
.31‐ 7.45 (m, 5H), 7.46‐ 7.52 (m, 1H). 13C NMR (CDCl
1
3
,
observed characterization data ( H) was consistent with the
1
50 MHz): 126.84, 127.62, 128.06, 128.55, 129.47, previous report in the literature.[4g]
1
1
29.97, 131.40, 132.54, 139.44, 140.56. MS (EI): found:
(
3q) 1, 1’:3, 1’’-Terphenyl.
+
1
88 (M ). The observed characterization data ( H) was
[
7]
consistent with the previous report in the literature.
The title compound was prepared according to the general
procedure as described above using benzene (20 mmol) and
m-xylene (0.25 mmol) as substrates. The crude mixture was
(
3m) 2-Bromobiphenyl
8
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
o
purified by flash column chromatography (hexane/ethyl and sonicated for 5 min and placed in an oil bath at 120 C
1
acetate, 95:5) to give the product 3q (42 mg, 65%). H as pre-heated. After reaction for 20h for methylbenzene, the
NMR (300 MHz, CDCl
.58 (m, 5H), 7.63-7.64 (m, 2H), 7.70-7.71 (m, 4H), 7.87 (d, washed with DCM (20 mL). 2M sodium hydroxide (2 mL)
3
): 7.42 (t, J = 3.6 Hz, 2H), 7.50- mixture was filtered through a short plug of silica gel and
7
J = 0.6 Hz, 1H). 13C NMR (CDCl
, 150 MHz):126.16,
26.20, 127.30, 127.44, 128.84, 129.22, 141.23, 141.83. MS
was added. The aqueous layer was extracted with
dichloromethane (3 X 20 mL), washed with water (30 mL)
then washed with brine (30 mL). The organic phase was
3
1
(
+
EI): found: 230 (M ). The observed characterization data
[
16]
2 4
dried over Na SO and concentrated under reduced pressure.
was consistent with the previous report in the literature.
The combined organic phase was concentrated under
reduced pressure. The product was purified using flash
(
3r) 1‐ Phenylnaphthalene
The title compound was prepared according to the general column chromatography on 200-300mesh silica gel with
procedure as described above using benzene (10 mmol) and hexane/ethyl acetate as an eluent.
1
-methylnaphthalene (0.25 mmol) as substrates. The crude
(
4
5a) Mixture of 2-chlorobiphenyl, 3-chlorobiphenyl and
-chlorobiphenyl.
mixture was purified by flash column chromatography
(
hexane/ethyl acetate, 92:8) to give the product 3r (31.1 mg,
1
The title compound was prepared according to the general
procedure as described above, and purified by flash column
chromatography (36.3 mg, 77%). The o : m : p ratio was
detected by GC-MS. MS (EI): found: 188 (M+).
6
9
1%). H NMR (300 MHz, DMSO-d
6
):  7.37 – 7.55 (m,
1
3
H), 7.73-7.76 (m, 1H), 7.89-7.97 (m, 2H). C NMR (75
MHz, CDCl3):  125.36, 125.74, 125.8, 126.00, 126.01,
1
1
26.90, 127.21, 127.61, 128.24, 130.06, 131.62, 133.79,
+
40.25, 140.76. MS (EI): found: 204 (M ).The observed
(
4
5b) Mixture of 2-bromobiphenyl, 3-bromobiphenyl and
-bromobiphenyl.
characterization data (1H) was consistent with that
previously reported in the literature.[19]
The title compound was prepared according to the general
procedure as described above, and purified by flash column
chromatography (49.5 mg, 81%). The o : m : p ratio was
detected by GC-MS. MS (EI): found: 232 (M+).
(
3s) 1, 1':2, 1''-Terphenyl
The title compound was prepared according to the general
procedure as described above using benzene (20 mmol) and
1
-2-dimethylbenzene (0.25 mmol) as substrates. The crude
(
5c) Mixture of 2-nitrobiphenyl, 3-nitrobiphenyl and 4-
mixture was purified was purified by flash column
chromatography (hexane/ethyl acetate, 95:5) to give the
product 3s (32.7 mg, 57%). The observed characterization
data are similar to 3o.
nitrobiphenyl
The title compound was prepared according to the general
procedure as described above, and purified by flash column
chromatography (41.2 mg, 83%).The o : m : p ratio was
detected by GC-MS. MS (EI): found: 199 (M+).
(
3t) 1, 1':4, 1''-Terphenyl
The title compound was prepared according to the general
procedure as described above using benzene (20 mmol) and
(
5d) Mixture of 1, 1':2, 1''-Terphenyl, 1, 1’:3, 1’’-
Terphenyl and 1, 1':4, 1''-Terphenyl
1
-4-dimethylbenzene (0.25 mmol) as substrates. The crude
mixture was purified by flash column chromatography
hexane/ethyl acetate, 95:5) to give the product (44.2mg,
7%). The observed characterization data are similar to 3j.
The title compound was prepared according to the general
procedure as described above, and purified by flash column
chromatography (50 mg, 87%).The o : m : p ratio was
detected by GC-MS. MS (EI): found: 230 (M+).
(
7
(
3u) 1, 1’:3, 1’’-Terphenyl.
General experimental procedure for intramolecular cross-
coupling product:
The title compound was prepared according to the general
procedure as described above using benzene (1.0 mL) and
m-xylene (0.25 mmol) as substrates. The crude mixture was
purified by flash column chromatography (hexane/ethyl
acetate) to give the product 3u (42 mg, 65%). The observed
characterization data are similar to 3q.
To an oven-dried 15 mL Ace pressure tubes equipped with a
Teflon coated magnetic stirbar, K
and 2-methylbenzophenone (0.25 mmol) and AgNO
2
S
2
O
8
(2.5 mmol, 675.7 g)
(35
3
mol%) were added. Then MeCN (2.0 ml) were added using
a syringe. The tube was sealed by a Teflon screwcap and
General experimental procedure for cross-coupling
between substituted arenes and methylbenzene:
o
sonicated for 5 min and placed in an oil bath at 120 C as
pre-heated. After reaction for 20 h, the mixture was filtered
through a short plug of silica gel and washed with DCM (20
mL). 2M sodium hydroxide (2 mL) was added. The aqueous
layer was extracted with dichloromethane (3 X 20 mL),
washed with water (30 mL) then washed with brine (30 mL).
To an oven-dried 4 mL Ace pressure tubes equipped with a
Teflon coated magnetic stirbar, K
methylbenzene (0.25 mmol), and AgNO
added. Then substituted arenes (5.0 mmol) and MeCN (1.0
mL) were added. The tube was sealed by a Teflon screwcap
2
S
2
O
8
(2 mmol) for
(35 mol%) were
3
The organic phase was dried over Na
2
SO
4
and concentrated
9
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
under reduced pressure. The product was purified using (DST/INSPIRE/04/2016/000247) and Early Carrier
flash column chromatography on 200-300 mesh silica gel Research Award (ECR/2017/000208). The Pohang
with hexane/ethyl acetate as an eluent.
University of Science and Technology, Pohang has filed a
patent on the catalysts reported herein.
(
7) 9H-fluoren-9-one.
The title compound was prepared according to the general
procedure as described above. Synthesized compound was
purified by flash column chromatography (22.9 mg, 51%).
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7
1
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3
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methylbenzene (0.25 mmol), AgNO
CH CN (1 ml). Separately, benzene/benzene-d
were added using a syringe. Then the tubes were sealed by a
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2
S
2
O
8
(2 mmol, 540.8 mg)
(35 mol%) and
(10 mmol)
3
3
6
o
o
oil bath at 120 C (pre-heated to 120 C). The reaction
mixture was allowed to heating for 20 h time. Purification
and separation procedures were followed by the above
methods.
Competitive reaction in same vessel: K
S
2 2
O
8
(2 mmol,
5
40.8 mg) and methylbenzene (0.25 mmol) were added to
3
pressure tubes (dried by a heat gun). AgNO (35 mol%) was
2
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(
3
1
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o
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Delhi, for the INSPIRE Faculty Award
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
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Advanced Synthesis & Catalysis
10.1002/adsc.201800213
FULL PAPER
Title Text Direct aryl-aryl coupling without pre-
functionalization enabled by excessive oxidation of
two-electron Ag(I)/Ag(III) catalyst
Adv. Synth. Catal. 2018, Volume, Page – Page
Ajay K. Singh, Min-Gyu Kim, Hyune-Jea Lee,
Rakhi Singh, Seung Hwan Cho, Dong-Pyo Kim*
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