Arenediazonium Tosylates (ADTs) as Efficient Reagents for Suzuki-Miyaura Cross-Coupling in Neat Water

Article abstract of DOI:10.1055/s-0036-1588919

A simple, convenient, and environment-friendly procedure for the preparation of substituted biaryls via Suzuki-Miyaura cross-coupling- was developed. The use of arenediazonium tosylates and corresponding boron compounds allows a conversion in neat water in the presence of commercially available Pd(OAc)₂ under mild conditions with tolerance to a wide range of functional groups. A procedure particularly useful for the synthesis of di-ortho-substituted biaryls was developed.

Full text of DOI:10.1055/s-0036-1588919

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2016, 48, A–I
paper
A
K. V. Kutonova et al.
Paper
Synthesis
Arenediazonium Tosylates (ADTs) as Efficient Reagents for Suzuki–
Miyaura Cross-Coupling in Neat Water
Ksenia V. Kutonovaa
Nicole Jungb,c
Marina E. Trusovaa
Victor D. Filimonova
Pavel S. Postnikov*d
Stefan Bräse*b,c
B(OH)2
R2
R2
N2+ –OTs
R1
R1
Pd(OAc)2, H2O, r.t.
27 examples
24–93% yield
a Department of Biotechnology and Organic Chemistry, National
Research Tomsk Polytechnic University, 634050 Tomsk, Russian
Federation
b Institute of Organic Chemistry, Karlsruhe Institute of Technology
(KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
braese@kit.edu
c Institute of Toxicology and Genetics, Karlsruhe Institute of Tech-
nology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-
Leopoldshafen, Germany
d Department of Technology of Organic substances and Polymer
materials, National Research Tomsk Polytechnic University,
634050 Tomsk, Russian Federation
postnikov@tpu.ru
Received: 28.10.2016
Accepted after revision: 31.10.2016
Published online: 29.11.2016
While aryl halides are the most typical substrate for this
transformation, the use of arenediazonium salts attracts
the ongoing interest due to their several advantages over
aryl halides in cross-coupling reactions.9 Following the
modern task to make the organic synthesis more environ-
ment-friendly, the new Suzuki–Miyaura coupling proce-
dures utilizing water as a solvent were developed.10 Howev-
er, only a few examples using arenediazonium salts in neat
water were described. Among them are the coupling of
arenediazonium silica-sulfates with sodium tetraphenylbo-
rate in the presence of Pd(OAc)2 and a base11 and the reac-
tion of arenediazonium tetrafluoroborates with potassium
aryltrifluoroborates, catalyzed by alginate/gellan-stabilized
Pd nanoparticles12 or PdCl2(MeCN)2.13 Whereas these meth-
ods allow synthesizing target biphenyls in mild conditions,
it is worth to note some drawbacks associated with them
such as the limited utility for the preparation of sterically
hindered biphenyls11 or the unavailability and expensive-
ness of the catalysts.12,13 Recently a new method based on
Pd/C-catalyzed reaction of arenediazonium tetrafluorobo-
rates and areneboronic acids in an aqueous hydrotropic
medium was developed.14 Though the presented method
allows for the preparation of a wide range of mono- and
disubstituted biaryls in high yields, it was shown that the
use of neat water instead of the aqueous hydrotropic medi-
um leads to a dramatic decrease of the product yield. Thus,
the Suzuki–Miyaura coupling using diazonium salts in neat
water with commercially available catalysts is still a poorly
described field, especially in the case of preparation of di-
ortho-substituted biphenyls.
DOI: 10.1055/s-0036-1588919; Art ID: ss-2016-z0633-op
Abstract A simple, convenient, and environment-friendly procedure
for the preparation of substituted biaryls via Suzuki–Miyaura cross-
coupling was developed. The use of arenediazonium tosylates and cor-
responding boron compounds allows a conversion in neat water in the
presence of commercially available Pd(OAc)2 under mild conditions
with tolerance to a wide range of functional groups. A procedure par-
ticularly useful for the synthesis of di-ortho-substituted biaryls was de-
veloped.
Key words Suzuki–Miyaura reactions, arenediazonium salts, arenedi-
azonium tosylates, water media, biphenyls
Biaryls play a pivotal role in the pharmaceutical indus-
try, materials science, and catalysis. Functionalized and ste-
rically hindered biaryls are considered to be attractive tar-
get structures, for example, due to the presence of these
structural motifs in a wide range of catalysts, drugs, and
advanced materials.1 Since Ullmann first reported on the
coupling reactions of aryl halides to biaryls,2 the new syn-
thetic procedures for aryl–aryl bond construction were in-
tensively studied.3 The most common of them are
Gomberg–Bachmann–Hey reaction,4 Gattermann synthe-
sis,5 oxidative arenes coupling,6 and Suzuki–Miyaura reac-
tion.7 Among these methods Suzuki–Miyaura cross-cou-
pling between aryl or heteroaryl electrophiles and boron
derivatives is regarded as a universal and easily controlled
method for biaryl synthesis.8
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

B
K. V. Kutonova et al.
Paper
Synthesis
Arenediazonium tosylates (ADTs) were easily synthe-
sized from the corresponding anilines and p-toluenesulfon-
ic acid; they are thermal and storage stable, and inexplo-
sive.15 The high solubility of ADTs in polar organic solvents
and water has favored to develop a wide range of synthetic
methods, having good advantages behind traditional arene-
diazonium tetrafluoroborates. Thus, the ADTs smoothly re-
act with halogen source followed by formation of appropri-
ate aryl halides.16 The ADTs have been shown to react
smoothly with azide ions under diverse conversions giving
aryl azides17 and furnishing appropriate products in Pd-
catalyzed reactions.18 Due to the high reactivity of ADTs in
aqueous media we were interested in their use in the
Suzuki–Miyaura coupling.
Table 1 Optimization of the Suzuki–Miyaura Coupling of Arenediazo-
nium Tosylate 1a with Phenylboronic Acid (2a)
N2+ –OTs
Ph
PhB(OH)2 2a
[Pd]
O2N
O2N
solvent, r.t.
N2
1a
3a
Entry Solvent
[Pd]
[Pd] (mol%) Time (h) Yield (%)a
1
2
THF
Pd(OAc)2
2
24
0.5
16
MeOH
1,4-dioxane
MeCN
H2O
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
2
17
3
2
48
120
48
46
4
2
tracesb
61
5
2
In this work, we present a new and mild procedure for
the synthesis of a wide range of biphenyls using commer-
cially available Pd(OAc)2 in neat water.
6
H2O
2
48
28c
60
7
H2O
1
72
To investigate the potential of the Suzuki–Miyaura cou-
pling with ADTs, the reaction of 4-nitrobenzenediazonium
tosylate (1a) with phenylboronic acid (2a) was used as a
model system. The cross-coupling conditions were opti-
mized regarding yield and reaction time using different sol-
vents, temperature and catalysts (Table 1). The reactions
were stopped instantly when the complete conversion of
the starting material was observed. First experiments with
2 mol% of Pd(OAc)2 in organic solvents (Table 1, entries 1–4)
yielded only low amounts of 4-nitrobiphenyl (3a), due to
the formation of the by-products biphenyl and nitroben-
zene. The reaction was shown to be very efficient when wa-
ter was used as solvent under the same conditions (entry
5). Attempts to further increase the yield by increasing the
temperature to 50 °C were not successful and caused the
appearance of side-products via homodimerization of the
phenylboronic acid (entry 6). It was shown that the amount
of Pd(OAc)2 can be reduced to 0.6 mol% without a remark-
able reduction of the yield (entries 7–9). In this case, how-
ever, the reaction time increased from 48 to 120 hours. Per-
forming the reaction in neat water at room temperature us-
ing 1 mol% of Pd(OAc)2 was chosen as the best trade-off for
the optimization of reaction rate and yield (entry 7). Other
catalysts such as Pd/C, PdCl2, and Pd(TFA)2 were tested as
well, but were shown to be less active than Pd(OAc)2 both in
water and methanol (entries 10–13).
To investigate the scope of the Suzuki–Miyaura reaction
of ADTs under the optimized reaction conditions (Table 1,
entry 7), a variety of ADTs 1 were allowed to react with
arylboronic acids 2 bearing different functional groups (Ta-
ble 2).
By using a diverse set of building blocks, it was shown
that the method described herein displays a general appli-
cability allowing a broad use of the Suzuki–Miyaura cou-
pling. The method tolerates diverse functional groups such
as ethers, esters, halides (bromine, fluorine), nitro, and
formyl. ADTs 1 both with electron-withdrawing (Table 2,
8
H2O
0.8
0.6
2
120
120
120
48
59
9
H2O
57
10
11
12
13
H2O
53
H2O
Pd/C
2
traces
43
MeOH
H2O
Pd/C
2
40
Pd(TFA)2
1
120
61
a Analytical yields according to GC analyses with internal reference (n-do-
decane).
b Complete conversion was not achieved.
c Reaction was performed at 50 °C.
entries 1–3, 5–14, 16, 17) and electron-donating groups
(entry 15) can arylate arylboronic acids 2 with different
substitution patterns giving moderate to high yields of the
desired biphenyls 3. Concerning the influence of the substi-
tution pattern of the arylboronic acids, no evident dif-
ferences of electron-withdrawing and electron-donating
groups were observed. To prove the synthetic utility of the
developed procedure, two selected examples were used in
upscaling experiments. It was shown that the results in a
lower mmol scale can be transferred very successfully to a
larger scale (experiments on 10, 20, and 50 mmol scale for
compounds 3a and 3h, entries 2, 10, 11).
The success of the previous reactions, which is even ob-
tained with ortho-substituted arylboronic acids or ortho-
substituted arenediazonium salts encouraged us to explore
the reaction to furnish di-ortho-functionalized biaryls. In
the literature, 2-substituted arenediazonium salts show less
or equal reactivity compared to 4- or 3-substituted
analogues.19 Using ADTs we were able to show that the
Suzuki–Miyaura coupling of ortho-substituted ADTs with
diverse arylboronic acids proceeds faster and the yields of
the target biphenyls are higher than comparable reactions
of para-substituted ADTs with the same arylboronic acids
(Table 2, entry 1 vs. 3 and entry 5 vs. 6). These findings en-
couraged us to develop a new ADT-based synthetic proce-
dure for the synthesis of 2,2′-disubstituted biphenyls (Table
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

C
K. V. Kutonova et al.
Paper
Synthesis
Table 2 Suzuki–Miyaura Coupling of Arenediazonium Tosylates 1 with
Arylboronic Acids 2
position (Table 3, entries 6–8 and 10, 11) demonstrated suf-
ficiently lower activity. The influence of the substituents of
the aryl boronic acids on the yield of the reaction are com-
parably low. Negligible effects could be observed indicating
that electron-donating groups in the benzene ring allow to
obtain target biphenyls in higher yields (e.g., entries 3, 4,
and 8).
B(OH)2
R2
N2+ –OTs
2
R2
R1
Pd(OAc)2 (1 mol%)
R1
3
H2O, r.t., N2
1
Table 3 Suzuki–Miyaura Coupling of ortho-Substituted Arenediazoni-
um Tosylates 1 with ortho-Substituted Areneboronic Acids 2
Entry ArN2+ –OTs
ArB(OH)2
Time (h) Product Yield (%)a
1
2
1a
1a
1b
1c
1d
1e
1a
1a
1a
1a
1a
1a
1a
1f
4-NO2
4-NO2
2-NO2
H
2a
2a
2a
2a
2a
2a
2b
2c
2d
2d
2d
2e
2f
H
72
72
12
48
48
16
20
240
72
72
72
20
16
24
72
72
30
3a
3a
3b
3c
3d
3e
3f
60
B(OH)2
R3
H
72b
76
N2+ –OTs
R2
2
R4
3
H
R3
R2
4
H
81
R1
Pd(OAc)2 (1 mol%)
H2O, r.t., N2
R4
1
R1
3
5
4-CO2Et
2-CO2Me
4-NO2
4-NO2
4-NO2
4-NO2
4-NO2
4-NO2
4-NO2
2-Br
H
54
6
H
58
Entry ArN2+ –OTs
ArB(OH)2
Time
(h)
Product Yield
(%)a
7
4-MeO
4-CHO
2-CHO
2-CHO
2-CHO
1-naphthyl
2-Me
H
67
8
3g
3h
3h
3h
3i
42c
68
1
2
1b
1b
1b
1b
1e
1f
2-NO2
2-NO2
2-NO2
2-NO2
2-CO2Me
2-Br
2g
2h
2i
2-F
5
160
4
3o
3p
3q
3r
92
58
83
89
72
36
24b
73
72
32b
36b
9
2-Cl
10
11
12
13
14
15
16
17
81d
91e
60
3
2,4-(MeO)2
2-MeO
2-F
4
2j
16
5
2g
2g
2g
2j
16
3s
3j
86
6
2-F
16
3t
2a
2a
2a
2a
3k
3l
65f
88f
30c
24
7
1h
1f
4-Br-2-F
2-Br
2-F
120
96
3u
3v
3w
3x
3y
1g
1h
1i
2-MeO
4-Br-2-F
4-F-2-Br
H
8
2-MeO
2-CF3O
2,4-(MeO)2
2,4-(MeO)2
H
3m
3n
9
1b
1h
1i
2-NO2
4-Br-2-F
4-F-2-Br
2k
2i
48
H
10
11
120
120
a Isolated yields.
b Reaction conducted at 10 mmol scale.
c Uncompleted conversion.
2i
a Isolated yields.
d Reaction conducted at 20 mmol scale.
e Reaction conducted at 50 mmol scale.
f Catalyst used: 2 mol%.
b Uncompleted conversion.
While cheap arylboronic acids were used for Suzuki–
Miyaura coupling with ADTs, it was shown that potassium
trifluoroboronates 4 can be used for such transformations
as well (Table 4). Potassium organotrifluoroborates were
used successfully in Suzuki–Miyaura type reactions be-
fore12,13,19b,22 and we expected the reactions to benefit from
the good solubility of the boronates in water. After the in-
vestigation of the PhBF3K-based reaction with several ADTs
we showed that PhBF3K (4a) can be used for Suzuki–Miyaura
coupling with ADT giving high yields of the target biphenyls
(Table 4). The reaction is fast and can be performed in the
presence of air. The potassium trifluoroboronate method
can be used as beneficial alternative to the method de-
scribed above. While para-substituted ADTs were less ac-
tive in the investigated Suzuki–Miyaura reactions in the
presence of boronic acids (Table 2, entries 1 and 3), the
same ADTs could be converted with PhBF3K very successful-
ly (Table 4, entries 1 and 2).
3). With the procedure developed herein for the coupling of
ADTs with arylboronic acids, we were able to synthesize a
range of 2,2′-disubstituted biphenyls in moderate to high
yields and good purity using mild reaction conditions in-
cluding the biphenyls 3x and 3y, which were synthesized
and characterized for the first time (Table 3). We assume
that the positive results of the coupling to 2,2′-disubstitut-
ed biphenyls can be explained by the ortho-effect in Pd-
catalyzed reactions which was previously discussed by
Widdowson20 and Felpin.21 Both groups found an enhance-
ment of the reaction rate in Suzuki–Miyaura reactions,
which was explained by the formation of cyclic Pd-com-
plexes via a coordinative bond between palladium and the
heteroatom in the coordinating group. The latter ortho-ef-
fects are supposed to cause the remarkably decreased reac-
tion time and better yields in case of ADTs with strong co-
ordinating groups in ortho-position as given in Table 3, en-
tries 1–5 and 9. ADTs with halogen substituents in 2-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

D
K. V. Kutonova et al.
Paper
Synthesis
Table 4 Suzuki–Miyaura Coupling of Arenediazonium Tosylates 1 with
Potassium Trifluoroboronates 4
Suzuki–Miyaura Reaction between Arenediazonium Tosylates
(ADTs) 1 and Arylboronic Acids 2; General Procedure
ADT 1 (1.0 mmol) synthesized by a previously reported method,16
was mixed with benzeneboronic acid 2 (1.2 mmol, 1.2 equiv) and
Pd(OAc)2 (1 mol%) under inert atmosphere (N2). Degassed H2O
(10 mL of water per 1 mmol ADT) was added under vigorous stirring.
The mixture was stirred at r.t. under N2 and the progress of the reac-
tion was monitored by TLC. The reaction was stopped when total con-
version of the ADT was observed. Then the mixture was extracted
with EtOAc (3 × 10 mL). The combined organic phases were washed
with brine (3 × 10 mL) and dried (anhyd Na2SO4). The solvent was re-
moved in vacuo to give the crude biphenyl, which was purified by col-
umn chromatography to give the pure product 3.
BF3K
R2
N2+ –OTs
4
R2
R1
Pd(OAc)2 (1 mol%)
H2O, r.t.
R1
1
3
Entry ArN2+ –OTs
ArBF3K
Time Product Yield
(h) (%)
1
2
3
4
5
6
1a
1b
1j
4-NO2
2-NO2
3-NO2
2-Br
4a
4a
4a
4a
4b
4a
H
H
H
H
12
3a
3b
3z
84
12
12
12
89
4-Nitrobiphenyl (3a)
Pale yellow powder; yield: 0.119 g (60%); mp 110–112 °C (Lit.23a mp
111–113 °C).
93
1f
3k
3aa
3l
69a
66
1a
1g
4-NO2
2-MeO
2-naphthyl 48
12
IR (ATR): 1928.7, 1592.9, 1574.1, 1505.8, 1477.2, 1402.7, 1337.2,
1156.9, 1102.2, 1077.3, 1004.9, 924.8, 850.7, 772.9, 737.0, 691.6,
H
85a
531.2, 474.9, 463.8, 401.2, 386.3 cm–1
.
a Catalyst used: 2 mol%.
1H NMR (CDCl3, 300 MHz): δ = 8.31 (m, 2 H), 7.75 (m, 2 H), 7.68–7.60
(m, 2 H), 7.55–7.43 (m, 3 H).
13C NMR (CDCl3, 75 MHz): δ = 147.6, 147.1, 138.8, 129.1 (2 C), 128.9,
127.8 (2 C), 127.4 (2 C), 124.1 (2 C).
MS (EI, 70 eV, 30 °C): m/z (%) = 199 (100, [M+]), 169 (33), 153 (24), 152
In conclusion, a new versatile method of Suzuki–Miyaura
cross-coupling reaction under mild conditions in neat wa-
ter was developed using easily synthesized, stable, and wa-
ter-soluble arenediazonium tosylates (ADTs). The presented
method tolerates many functional groups such as halides,
esters and others and allows, due to the ortho-effect of co-
ordinating groups, the preparation of a wide range of 2,2′-
disubstituted biphenyls under mild conditions at room
temperature. The procedure was shown to work in very
good yields for selected examples up to gram scales. The
method was extended to the use of potassium organotri-
fluoroborates in combination with ADTs very successfully
to give an alternative procedure including commercially
available boron building blocks.
(71), 151 (14), 141 (26), 115 (10), 77 (3), 51 (1).
HRMS (EI): m/z calcd for C12H9NO2: 199.0628; found: 199.0627.
2-Nitrobiphenyl (3b)
Pale yellow powder; yield: 0.151 g (76%); mp 38 °C (Lit.23b mp 37 °C).
IR (ATR): 3061.1, 1604.2, 1568.0, 1520.3, 1471.5, 1450.9, 1351.0,
1074.5, 1008.3, 851.9, 769.7, 738.7, 697.5, 666.0, 612.1, 577.7, 514.8,
401.7 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 7.87 (m, 1 H), 7.68–7.58 (m, 1 H), 7.55–
7.39 (m, 5 H), 7.38–7.30 (m, 2 H).
13C NMR (CDCl3, 75 MHz): δ = 149.2, 137.3, 136.3, 132.2, 131.9, 128.6
(2 C), 128.2, 128.1, 127.8 (2 C), 124.0.
MS (EI, 70 eV, 30 °C): m/z (%) = 199 (70, [M+]), 182 (44), 171 (52), 170
(17), 152 (100), 151 (32), 143 (31), 115 (54), 76 (20), 63 (9), 51 (8).
1H NMR spectra were recorded on a Bruker 250 (250 MHz), Bruker
300 (300 MHz), or a Bruker AM 400 (400 MHz) and Bruker AM 500
(500 MHz) spectrometer. 13C NMR spectra were recorded on Bruker
250 (63 MHz), Bruker 300 (75 MHz), and Bruker AM 400 (100 MHz)
spectrometers. MS (EI) (electron ionization mass spectrometry): Fin-
nigan MAT 90 (70 eV). IR: ATR spectra were recorded by diamond
crystal on Bruker ALPHA-IR. Routine monitoring of reactions were
performed using silica gel coated aluminum plates (Merck, silica gel
60, F254), which were analyzed under UV-light at 254 nm and dipped
into a solution of 2-naphthol (5% naphthol in aq 10% NaOH, dipping
solution). Solvent mixtures are understood as volume/volume. Sol-
vents, reagents and chemicals were purchased from Sigma-Aldrich,
Alfa Aesar, ABCR, and VWR. Solvents, reagents, and chemicals were
used as purchased, unless stated otherwise.
HRMS (EI): m/z calcd for C12H9NO2: 199.0628; found: 199.0626.
Biphenyl (3c)
White powder; yield: 0.125 g (81%); mp 70–71 °C (Lit.23a mp 70 °C).
IR (ATR): 3031.4, 1567.9, 1476.3, 1427.6, 1343.5, 1169.1, 1089.9,
1040.2, 1004.5, 901.9, 724.5, 692.3, 608.7, 454.9 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 7.75–7.66 (m, 4 H), 7.60–7.50 (m, 4 H),
7.49–7.41 (m, 2 H).
13C NMR (CDCl3, 75 MHz): δ = 141.3 (2 C), 128.7 (4 C), 127.2 (2 C),
127.1 (4 C).
MS (EI, 70 eV, 60 °C): m/z (%) = 154 (100, [M+]), 77 (15), 76 (20), 63 (6),
51 (9).
Synthesis of Biphenyls via Suzuki–Miyaura Reaction of ADTs
HRMS (EI): m/z calcd for C12H10: 154.0778; found: 154.0777.
CAUTION! In our two laboratories there was no case of sudden de-
composition during the preparation, purification, and handling of
salts 1a–i. Nevertheless it must be kept in mind that in general diazo-
nium salts in the dry state are potentially explosive. Therefore they
must be carefully stored and handled.
Ethyl 4-Phenylbenzoate (3d)
White powder; yield: 0.122 g (54%); mp 48–50 °C (Lit.23c mp 49–
50 °C).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

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K. V. Kutonova et al.
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Synthesis
IR (ATR): 2982.0, 1703.9, 1605.2, 1472.3, 1448.4, 1404.0, 1364.4,
1312.9, 1267.9, 1200.0, 1178.1, 1111.5, 1024.1, 1004.0, 856.2, 743.6,
IR (ATR): 3076.5, 2921.0, 2850.2, 1681.7, 1589.9, 1509.5, 1471.4,
1397.0, 1346.8, 1316.4, 1298.6, 1250.8, 1193.7, 1158.0, 1106.9,
1003.4, 863.5, 826.1, 770.5, 747.1, 699.1, 665.2, 636.6, 624.5, 548.4,
696.8, 509.7, 4670, 444.3 cm–1
.
510.8, 435.8 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 8.18–8.15 (m, 1 H), 8.14–8.11 (m, 1 H),
7.73–7.61 (m, 4 H), 7.53–7.37 (m, 3 H), 4.42 (q, J = 7.2 Hz, 2 H), 1.42 (t,
J = 7.0 Hz, 3 H).
1H NMR (CDCl3, 300 MHz): δ = 9.97 (s, 1 H), 8.35 (m, 2 H), 8.07 (m,
1 H), 7.77–7.67 (m, 1 H), 7.65–7.54 (m, 3 H), 7.44 (m, 1 H).
13C NMR (CDCl3, 75 MHz): δ = 166.4, 145.5, 140.0, 130.0 (2 C), 129.3,
13C NMR (CDCl3, 75 MHz): δ = 191.0, 147.7, 144.8, 142.9, 133.9, 133.6,
128.8 (2 C), 128.0, 127.2 (2 C), 126.9 (2 C), 60.9, 14.3.
130.8 (2 C), 130.6, 129.1, 128.9, 123.6 (2 C).
MS (EI, 70 eV, 40 °C): m/z (%) = 226 (100, [M+]), 198 (29), 181 (69), 153
(7), 69 (1).
MS (EI, 70 eV, 50 °C): m/z (%) = 227 (100, [M+]), 210 (26), 180 (68), 169
(22), 152 (69), 131 (11), 119 (13), 104 (16), 76 (12), 69 (69), 57 (11),
43 (6).
HRMS (EI): m/z calcd for C15H14O2: 226.0989; found: 226.0988.
HRMS (EI): m/z calcd for C13H9NO3: 227.0577; found: 227.0576.
Methyl 2-Phenylbenzoate (3e)
White powder; yield: 0.123 g (58%); mp 111–112 °C (Lit.23d mp 110–
111 °C).
1-(4-Nitrophenyl)naphthalene (3i)
Pale yellow powder; yield: 0.15 g (60%); mp 128 °C (Lit.23h mp 128–
129 °C).
IR (ATR): 2948.1, 1717.7, 1597.0, 1476.3, 1429.3, 1279.3, 1244.2,
1188.2, 1123.8, 1087.2, 1048.1, 1007.6, 962 cm–1
.
IR (ATR): 2921.9, 1595.7, 1510.5, 1394.8, 1345.3, 1249.2, 1103.1,
1014.9, 959.5, 857.3, 823.1, 801.2, 777.4, 753.4, 715.1, 698.1, 643.7,
1H NMR (CDCl3, 300 MHz): δ = 7.85 (m, 1 H), 7.60–7.49 (m, 1 H), 7.47–
7.32 (m, 7 H), 3.66 (s, 3 H).
13C NMR (CDCl3, 75 MHz): δ = 169.1, 142.4, 141.3, 131.2, 130.8, 130.7,
129.7, 128.3, 128.0, 127.2, 127.1, 51.9.
570.4, 555.9, 494.0, 435.5, 405.0 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 8.38 (m, 2 H), 7.95 (m, 2 H), 7.80 (m, 1
H), 7.73–7.65 (m, 2 H), 7.61–7.41 (m, 4 H).
13C NMR (CDCl3, 75 MHz): δ = 137.8, 133.8, 130.9 (2 C), 129.0, 128.6,
127.1, 126.7, 126.2, 125.3, 125.1, 123.6 (2 C) (3 quaternary carbons
could not be observed).
HRMS (EI): m/z calcd for C14H12O2: 212.0832; found: 212.0830.
4-Methoxy-4′-nitrobiphenyl (3f)
Yellow powder; yield: 0.153 g (67%); mp 109–110 °C (Lit.23e mp 108–
110 °C).
MS (EI, 70 eV, 90 °C): m/z (%) = 249 (100 [M+]), 202 (55), 101 (4), 43
(4).
HRMS (EI): m/z calcd for C16H11NO2: 249.0785; found: 249.0784.
IR (ATR): 2927.5, 2834.3, 1598.5, 1504.5, 1340.5, 1300.1, 1272.9,
1249.4, 1180.9, 1105.8, 1032.2, 1014.5, 861.5, 828.7, 814.3, 755.0,
721.3, 695.2, 603.4, 549.8, 529.1, 492.1, 431.1 cm–1
.
2-Methyl-4′-nitrobiphenyl (3j)
Pale yellow powder; yield: 0.183 g (86%); mp 103–104 °C (Lit.23i mp
104–105 °C).
1H NMR (CDCl3, 300 MHz): δ = 8.32–8.21 (m, 2 H), 7.74–7.65 (m, 2 H),
7.63–7.54 (m, 2 H), 7.08–6.97 (m, 2 H), 3.88 (s, 3 H).
IR (ATR): 2922.7, 1594.0, 1508.1, 1478.2, 1454.4, 1401.5, 1384.9,
1342.5, 1197.5, 1103.8, 1030.9, 1005.1, 875.9, 854.1, 832.2, 804.1,
13C NMR (CDCl3, 75 MHz): δ = 160.4, 147.2, 146.5, 131.0, 128.5 (2 C),
127.0 (2 C), 124.1 (2 C), 114.6 (2 C), 55.4.
MS (EI, 70 eV, 50 °C): m/z (%) = 229 (100, [M+]), 219 (30), 199 (36), 180
(15), 171 (22), 169 (32), 152 (17), 143 (9), 131 (10), 119 (14), 115 (11),
69 (42).
773.2, 750.5, 726.7, 697.8, 560.3, 532.7, 505.9, 464.2, 450.6, 399.2 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 8.40–8.25 (m, 2 H), 7.61–7.51 (m, 2 H),
7.41–7.24 (m, 4 H), 2.34 (s, 3 H).
13C NMR (CDCl3, 75 MHz): δ = 148.8, 146.9, 139.6, 135.0, 130.7, 130.1
(2 C), 129.4, 128.4, 126.1, 123.4 (2 C), 20.2.
HRMS (EI): m/z calcd for C13H11NO3: 229.0732; found: 229.0733.
MS (EI, 70 eV, 60 °C): m/z (%) = 213 (100, [M+]), 183 (5), 165 (28), 152
(21), 128 (4), 115 (3), 43 (1).
4-(4-Nitrophenyl)benzaldehyde (3g)
Pale yellow powder; yield: 0.09 g (42%); mp 127–129 °C (Lit.23f mp
HRMS (EI): m/z calcd for C13H11NO2: 213.0785, found: 213.0784.
128–130 °C).
IR (ATR): 3070.2, 2820.6, 1691.3, 1597.0, 1567.2, 1503.4, 1425.7,
1385.0, 1337.4, 1203.8, 1169.9, 1107.4, 1002.6, 855.5, 817.0, 752.0,
2-Bromobiphenyl (3k)
718.9, 691.0, 665.0, 534.7, 476.8, 395.2 cm–1
.
Yellow oil; yield: 0.139 g (65%).
1H NMR (CDCl3, 300 MHz): δ = 10.10 (s, 1 H), 8.37–8.28 (m, 2 H),
8.05–7.98 (m, 2 H), 7.80 (m, 4 H).
13C NMR (CDCl3, 75 MHz): δ = 191.6, 147.7, 146.0, 144.4, 136.2, 130.4
(2 C), 128.2 (2 C), 128.0 (2 C), 124.2 (2 C).
IR (ATR): 3053.7, 1577.5, 1481.1, 1463.0, 1446.3, 1420.2, 1118.6,
1067.7, 1025.8, 1005.4, 768.3, 745.4, 697.9, 660.2, 611.5, 551.8, 449.9
cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 7.69 (m, 1 H), 7.62 (m, 1 H), 7.45–7.34
(m, 6 H), 7.26–7.18 (m, 1 H).
13C NMR (75 MHz, CDCl3): δ = 142.6, 141.1, 133.1, 131.2, 129.3, 128.7,
MS (EI, 70 eV, 40 °C): m/z (%) = 227 (23, [M+]), 219 (22), 181 (23), 169
(32), 152 (18), 131 (28), 119 (29), 100 (7), 69 (100).
128.7, 127.9, 127.6, 127.3, 127.2, 127.1.
MS (EI, 70 eV, 50 °C): m/z (%) = 234/232 (62/62, [M+]), 152 (100), 126
HRMS (EI): m/z calcd for C13H9NO3: 227.0577; found: 227.0578.
(12), 76 (37), 51 (3).
2-(4-Nitrophenyl)benzaldehyde (3h)
HRMS (EI): m/z calcd for C12H979Br: 231.9886; found: 213.9882.
Pale yellow powder; yield: 0.154 g (68%); mp 119 °C (Lit.23g mp 118–
120 °C).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

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K. V. Kutonova et al.
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Synthesis
2-Methoxybiphenyl (3l)
1H NMR (CDCl3, 300 MHz): δ = 8.07 (m, 1 H), 7.71–7.62 (m, 1 H), 7.59–
Pale yellow powder; yield: 0.162 g (88%); mp 34–35 °C (Lit.23j mp 31–
33 °C).
7.50 (m, 1 H), 7.48–7.39 (m, 1 H), 7.37–7.23 (m, 4 H).
13C NMR (CDCl3, 75 MHz): δ = 148.6, 137.1, 134.3, 133.0, 132.6, 132.3,
129.8, 129.4, 129.3, 129.0, 126.9, 124.3.
IR (ATR): 3060.2, 1598.2, 1568.2, 1522.1, 1471.8, 1429.7, 1351.5,
1258.0, 1235.1, 1121.7, 1074.2, 1026.0, 1008.2, 851.9, 769.6, 738.7,
HRMS (EI): m/z calcd for C12H8ClNO2: 233.0244; found: 233.0242.
697.5, 666.1, 611.8, 541.1, 401.0 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 7.65–7.54 (m, 2 H), 7.52–7.44 (m, 2 H),
2,4-Dimethoxy-2′-nitrobiphenyl (3q)
Pale yellow powder; yield: 0.215 g (83%); mp 99–101 °C (Lit.23m mp
101–102 °C).
7.42–7.33 (m, 3 H), 7.15–7.00 (m, 2 H), 3.86 (s, 3 H).
13C NMR (CDCl3, 75 MHz): δ = 156.4, 138.5, 130.8, 130.7, 129.5 (2 C),
128.6, 127.9 (2 C), 126.9, 120.8, 111.2, 55.5.
MS (EI, 70 eV, 30 °C): m/z (%) = 184 (100, [M+]), 169 (83), 152 (19), 141
(67), 115 (65), 91 (10), 76 (4), 39 (4).
IR (ATR): 2831.7, 1613.4, 1584.7, 1508.8, 1452.4, 1414.9, 1344.9,
1306.4, 1277.5, 1258.5, 1238.2, 1205.4, 1158.0, 1133.0, 1085.2,
1054.1, 1023.1, 966.6, 915.0, 854.5, 840.5, 810.3, 789.2, 758.7, 703.5,
657.0, 634.6, 602.1, 568.6, 469.3 cm–1
.
HRMS (EI): m/z calcd for C13H12O: 184.0883; found: 184.0884.
1H NMR (CDCl3, 300 MHz): δ = 7.90 (m, 1 H), 7.65–7.58 (m, 1 H), 7.47–
7.38 (m, 2 H), 7.25 (m, 1 H), 6.62 (m, 1 H), 6.49 (m, 1 H), 3.86 (s, 3 H),
3.69 (s, 3 H).
13C NMR (CDCl3, 75 MHz): δ = 161.4, 157.0, 149.8, 132.9, 132.5 (2 C),
130.2, 127.6, 123.8, 119.7, 105.2, 98.7, 55.4, 55.1.
4-Bromo-2-fluorobiphenyl (3m)
White powder; yield: 0.075 g (30%); mp 35 °C (Lit.23k mp 35–36 °C).
1H NMR (CDCl3, 250 MHz): δ = 7.53–7.25 (m, 8 H).
13C NMR (CDCl3, 63 MHz): δ = 159.5, 134.8, 131.7, 128.8, 128.5, 128.4,
128.1, 128.0, 127.7, 121.3, 119.7.
HRMS (EI): m/z calcd for C12H879BrF: 249.9788; found: 249.9786.
MS (EI, 70 eV, 20 °C): m/z (%) = 259 (100, [M+]), 228 (3), 199 (4), 185
(1), 169 (1), 58 (1).
HRMS (EI): m/z calcd for C14H13NO4: 259.0841; found: 259.0839.
2-Bromo-4-fluorobiphenyl (3n)
2-Methoxy-2′-nitrobiphenyl (3r)
Pale yellow powder; yield: 0.204 g (89%); mp 76–78 °C (Lit.23n mp
79 °C).
White oil; yield: 0.06 g (24%).
IR (ATR): 3063, 1595, 1504, 1474, 1444, 1381, 1255, 1198, 1056, 1031,
1007, 868, 819, 762, 698, 670, 580, 553, 469, 440 cm–1
.
IR (ATR): 3065.0, 2934.3, 2835.8, 1607.5, 1583.7, 1523.0, 1497.3,
1460.7, 1429.8, 1354.7, 1284.3, 1247.6, 1179.9, 1161.9, 1121.9,
1088.8, 1052.6, 1024.0, 853.7, 800.7, 784.8, 753.5, 740.3, 704.6, 665.1,
1H NMR (CDCl3, 400 MHz): δ = 7.49–7.36 (m, 6 H), 7.32 (m, 1 H), 7.10
(m, 1 H).
13C NMR (CDCl3, 63 MHz): δ = 161.6, 140.2, 138.9, 132.0, 129.4, 128.0,
613.1, 560.8, 403.7 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 8.00 (m, 1 H), 7.73–7.66 (m, 1 H), 7.56–
7.38 (m, 4 H), 7.19–7.13 (m, 1 H), 6.99 (m, 1 H), 3.77 (s, 3 H).
127.7, 122.7, 120.2, 114.5.
19F NMR (CDCl3, 376 MHz): δ = –113.5 (br s).
13C NMR (CDCl3, 75 MHz): δ = 156.4, 150.2, 133.6, 133.1, 132.9, 130.2,
MS (EI, 70 eV, 30 °C): m/z (%) = 252/250 (87/90), 170 (100), 151 (14),
130.1, 128.4, 127.5, 124.3, 121.6, 111.1, 55.6.
144 (10), 125 (6), 99 (6), 85 (23), 76 (4), 63 (4).
MS (EI, 70 eV, 50 °C): m/z (%) = 229 (100, [M+]), 214 (39), 198 (4), 184
HRMS (EI): m/z calcd for C12H879BrF: 249.9788; found: 249.9786.
(4), 170 (6), 168 (7), 152 (3), 140 (3), 128 (5), 115 (7), 89 (2), 77 (3).
2-Fluoro-2′-nitrobiphenyl (3o)
HRMS (EI): m/z calcd for C13H11NO3: 229.0733; found: 229.0733.
Yellow powder; yield: 0.199 g (92%); mp 70–72 °C (Lit.23l mp 71–
72 °C).
Methyl 2′-Fluoro-[1,1′-biphenyl]-2-carboxylate (3s)
Colorless oil; yield: 0.166 g (72%).
IR (ATR): 2924.7, 1606.8, 1580.7, 1519.2, 1497.7, 1470.9, 1449.5,
1434.8, 1351.0, 1280.3, 1243.1, 1202.6, 1109.2 1087.7, 1004.9, 956.6,
908.2, 854.6, 820.3, 784.1, 762.6, 746.9, 722.2, 701.0, 662.6, 611.2,
IR (ATR): 2949.4, 1722.5, 1597.5, 1583.4, 1500.5, 1480.2, 1431.4,
1287.7, 1258.2, 1207.2, 1126.7, 1107.9, 1084.9, 1049.1, 1006.9, 962.6,
830.1, 818.3, 798.3, 753.3, 728.9, 708.6, 661.6, 615.6, 567.0, 520.2,
582.1, 564.3, 519.6, 486.6, 444.1, 396.6 cm–1
.
444.4 cm–1
.
1H NMR (CDCl3, 400 MHz): δ = 8.05 (m, 1 H), 7.72–7.65 (m, 1 H), 7.56
(m, 1 H), 7.46 (m, 1 H), 7.44–7.38 (m, 1 H), 7.36 (m, 1 H), 7.26 (m, 1
H), 7.13 (m, 1 H).
1H NMR (CDCl3, 400 MHz): δ = 8.02 (m, 1 H), 7.63–7.56 (m, 1 H), 7.48
(m, 1 H), 7.41–7.30 (m, 3 H), 7.26–7.21 (m, 1 H), 7.16–7.10 (m, 1 H),
3.73 (s, 3 H).
13C NMR (CDCl3, 100 MHz): δ = 159.6, 149.3, 133.2, 132.8, 130.9,
13C NMR (CDCl3, 100 MHz): δ = 167.7, 159.4, 136.4, 131.7, 131.3,
130.6, 130.4, 130.0, 129.1, 129.0, 127.8, 123.9, 114.9, 51.8.
130.5, 130.3, 129.2, 125.9, 124.9, 124.8, 115.8.
19F NMR (CDCl3, 376 MHz): δ = –116.0 (s).
19F NMR (CDCl3, 376 MHz): δ = –116.6 (s).
MS (EI, 70 eV, 20 °C): m/z (%) = 217 (78), 189 (21), 170 (100), 159 (24),
MS (EI, 70 eV, 50 °C): m/z (%) = 230 (81, [M+]), 211 (9), 199 (100), 170
151 (13), 133 (33), 115 (9), 69 (4).
(50), 151 (8).
HRMS (EI): m/z calcd for C12H8FNO2: 217.0533; found: 217.0534.
HRMS (EI): m/z calcd for C14H11FO2: 230.0738; found: 230.0737.
2-Chloro-2′-nitrobiphenyl (3p)
Pale yellow powder; yield: 0.135 g (58%); mp 71 °C (Lit.23l mp 71–
72 °C).
2-Bromo-2′-fluorobiphenyl (3t)
Colorless oil; yield: 0.09 g (36%).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

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Synthesis
IR (ATR): 3063.0, 1581.0, 1554.9, 1496.9, 1463.0, 1405.8, 1246.3,
1208.9, 1109.0, 1073.7, 1041.7, 1021.2, 996.0, 884.9, 827.4, 784.8,
IR (ATR): 2936, 2835, 1598, 1513, 1477, 1437, 1392, 1307, 1282, 1253,
1206, 1158, 1136, 1117, 1072, 1032, 1004, 934, 867, 821, 797, 699,
751.0, 728.4, 689.3, 662.5, 614.4, 522.0, 492.4, 456.0, 427.0 cm–1
.
637, 579, 504, 456 cm–1
.
1H NMR (CDCl3, 400 MHz): δ = 7.71 (m, 1 H), 7.54–7.47 (m, 2 H), 7.42
1H NMR (CDCl3, 400 MHz): δ = 7.34–7.30 (m, 2 H), 7.25–7.21 (m, 1 H),
(m, 1 H), 7.39–7.30 (m, 2 H), 7.26–7.20 (m, 1 H), 7.17 (m, 1 H).
7.18–7.16 (m, 1 H), 6.60–6.57 (m, 2 H), 3.87 (s, 3 H), 3.80 (s, 3 H).
13C NMR (CDCl3, 100 MHz): δ = 159.6, 137.8, 131.9, 130.6, 130.6,
13C NMR (CDCl3, 100 MHz): δ = 161.1, 159.4, 158.7, 133.0, 131.5,
129.9, 129.6, 129.6, 127.7, 124.5, 122.4, 116.2.
127.0, 125.0, 120.7, 119.1, 116.5, 104.5, 98.8, 55.6, 55.4.
19F NMR (CDCl3, 376 MHz): δ = –117.8 (s).
19F NMR (CDCl3, 376 MHz): δ = –111.3 (s).
MS (EI, 70 eV, 50 °C): m/z (%) = 252/250 (98/100, [M+]), 170 (67), 151
(10), 144 (4), 125 (6), 75 (2).
HRMS (EI): m/z calcd for C12H879BrF: 249.9786; found: 249.9788.
MS (EI, 70 eV, 20 °C): m/z (%) = 312/310 (24/24, [M+]), 252/250
(98/100), 234/232 (29/30), 170 (70), 154/152 (37/33), 144 (7), 126
(10), 85 (16), 76 (12), 63 (6), 51 (6).
HRMS (EI): m/z calcd for C14H1279BrFO2: 309.9999; found: 310.0000.
4-Bromo-2-fluoro-2′-fluorobiphenyl (3u)
2-Bromo-4-fluoro-2′,4′-dimethoxybiphenyl (3y)
Colorless oil; yield: 0.064 g (24%).
Colorless oil; yield: 0.112 g (36%).
1H NMR (CDCl3, 400 MHz): δ = 7.40–7.31 (m, 4 H), 7.24–7.11 (m, 3 H).
IR (ATR): 2936.5, 2834.1, 1593.6, 1513.9, 1477.7, 1435.9, 1415.2,
1306.0, 1281.1, 1263.7, 1206.6, 1150.2, 1033.1, 1002.2, 933.2, 866.4,
13C NMR (CDCl3, 75 MHz): δ = 159.7, 159.6, 132.6, 131.4–131.3, 130.1,
127.5, 124.2, 122.6, 122.6, 122.2, 119.5, 115.9.
19F NMR (CDCl3, 376 MHz): δ = –114.6 to –114.7 (m), –111.7 to –111.8
(m).
MS (EI, 70 eV, 50 °C): m/z (%) = 270/268 (98/100, [M+]), 188 (60), 169
(15), 162 (3), 135 (5), 94 (12), 84 (4).
HRMS (EI): m/z calcd for C12H779BrF2: 267.9694; found: 267.9695.
821.2, 761.9, 686.4, 635.4, 577.4, 528.0, 448.1 cm–1
.
1H NMR (CDCl3, 400 MHz): δ = 7.46–7.42 (m, 1 H), 7.32–7.29 (m, 1 H),
7.13–7.08 (m, 2 H), 6.63–6.60 (m, 2 H), 3.93–3.91 (m, 3 H), 3.83–3.82
(m, 3 H).
13C NMR (CDCl3, 100 MHz): δ = 161.5, 160.9, 157.7, 135.7, 132.6,
131.4, 124.8, 122.2, 119.6, 114.1, 104.1, 98.8, 55.6, 55.4.
19F NMR (CDCl3, 376 MHz): δ = –114.0 (s).
2-Bromo-2′-methoxybiphenyl (3v)
MS (EI, 70 eV, 50 °C): m/z (%) = 312/310 (100/100, [M+]), 268 (7), 229
(9), 216 (88), 201 (38), 186 (11), 173 (20), 157 (29), 152 (17), 145 (12),
125 (5), 69 (3).
Colorless oil; yield: 0.191 g (73%).
IR (ATR): 2929, 2833, 1598, 1580, 1495, 1449, 1430, 1275, 1247, 1226,
1163, 1126, 1113, 1064, 10477, 1020, 1001, 937, 801, 755, 658, 612,
HRMS (EI): m/z calcd for C14H1279BrFO2: 309.9999; found: 309.9998.
554, 500, 437 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 7.66–7.59 (m, 1 H), 7.40–7.23 (m, 3 H),
7.21–7.11 (m, 2 H), 7.04–6.91 (m, 2 H), 3.75 (s, 3 H).
13C NMR (CDCl3, 75 MHz): δ = 156.5, 139.8, 132.4, 131.5, 130.8, 130.2,
129.3, 128.6, 127.0, 124.2, 120.3, 110.9, 55.5.
Suzuki–Miyaura Reaction Between Arenediazonium Tosylates
(ADTs) 1 and Potassium Benzenetrifluoroborate 4; General Proce-
dure
To a solution of ADT 1 (1.0 mmol), synthesized by a previously report-
ed method,16 in H2O (10 mL of H2O per 1 mmol ADT) were added po-
tassium benzenetrifluoroborate 4 (1.2 mmol, 1.2 equiv) and Pd(OAc)2
(1 mol%). The mixture was stirred at r.t. and the progress of the reac-
tion was monitored by TLC. The reaction was stopped when total con-
version of the ADT was observed. Then the mixture was extracted
with EtOAc (3 × 10 mL). The combined organic phases were washed
with brine (3 × 10 mL), dried (anhyd Na2SO4) and the solvent was re-
moved in vacuo to give the crude biphenyls, which were purified by
column chromatography to give the pure products 3a, 3b, 3k, 3l, 3z,
3aa, respectively.
MS (EI, 70 eV, 50 °C): m/z (%) = 262 (37, [M+]), 183 (59), 168 (100), 152
(14), 139 (27), 114 (4), 76 (3).
HRMS (EI): m/z calcd for C13H1179BrO: 261.9988; found: 261.9989.
2-Nitro-2′-(trifluoromethoxy)biphenyl (3w)
Yellow powder; yield: 0.204 g (72%); mp 74–76 °C (Lit.23o mp 73–
74 °C).
IR (ATR): 1611.4, 1572.2, 1525.1, 1501.2, 1472.7, 1449.2, 1351.1,
1244.6, 1215.2, 1166.2, 1114.2, 1008.2, 923.2, 853.3, 820.0, 786.0,
761.9, 742.2, 703.2, 665.9, 631.0, 609.6, 578.9, 555.2, 410.4 cm–1
.
1H NMR (CDCl3, 400 MHz): δ = 8.08 (m, 1 H), 7.69 (m, 1 H), 7.57 (m, 1
4-Nitrobiphenyl (3a)
Pale yellow powder; yield: 0.167 g (84%); mp 110–112 °C (Lit.23a mp
111–113 °C).
H), 7.50–7.37 (m, 4 H), 7.36–7.31 (m, 1 H).
13C NMR (CDCl3, 100 MHz): δ = 148.8, 146.0, 132.9, 132.5, 131.6,
131.5, 130.3, 129.7, 129.0, 127.1, 124.4, 120.5, 120.2.
19F NMR (CDCl3, 376 MHz): δ = –57.6 (s).
MS (EI, 70 eV, 30 °C): m/z (%) = 283 (82, [M+]), 198 (100), 170 (54), 168
2-Nitrobiphenyl (3b)
Pale yellow powder; yield: 0.177 g (89%); mp 38 °C (Lit.23b mp 37 °C).
(63), 139 (45), 115 (14), 69 (12).
2-Bromobiphenyl (3k)
HRMS (EI): m/z calcd for C13H8F3NO3: 283.0450; found: 283.0451.
Yellow oil; yield: 0.148 g (69%).
4-Bromo-2-fluoro-2′,4′-dimethoxybiphenyl (3x)
2-Methoxybiphenyl (3l)
Pale yellow powder; yield: 0.156 g (85%); mp 34–35 °C (Lit.23j mp 31–
Colorless oil; yield: 0.1 g (32%).
33 °C).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

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3-Nitrobiphenyl (3z)
Pale yellow powder; yield: 0.185 g (93%); mp 56–58 °C (Lit.23a mp 57–
59 °C).
A.; Chen, Y.; Kucukguzel, S. G. Front. Biosci. 2008, 13, 3857.
(d) Meegalla, S. K.; Wall, M. J.; Chen, J.; Wilson, K. J.; Ballentine,
S. K.; Desjarlais, R. L.; Schubert, C.; Crysler, C. S.; Chen, Y.;
Molloy, C. J.; Chaikin, M. A.; Manthey, C. L.; Player, M. R.;
Tomczuk, B. E.; Illig, C. R. Bioorg. Med. Chem. Lett. 2008, 18,
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Pharm. Bull. 1992, 40, 240.
IR (ATR): 2920.6, 2851.1, 1521.3, 1498.9, 1453.1, 1347.2, 1291.6,
1079.7, 1043.2, 895.8, 874.5, 811.0, 764.7, 728.9, 693.6, 680.1, 671.3,
609.0, 474.8, 411.0 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 8.47 (s, 1 H), 8.21 (m, 1 H), 7.93 (m, 1
H), 7.68–7.57 (m, 3 H), 7.55–7.41 (m, 3 H).
13C NMR (CDCl3, 75 MHz): δ = 148.7, 142.9, 138.6, 133.0, 129.7, 129.1
(2 C), 128.5, 127.1 (2 C), 122.0, 121.9.
(2) Ullmann, F.; Tcherniack, J. Ber. Dtsch. Chem. Ges. 1905, 38, 4110.
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2447.
(4) Gomberg, M.; Bachmann, W. E. J. Am. Chem. Soc. 1924, 46, 2339.
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9633. (b) Alonso, F.; Beletskaya, I. P.; Yus, M. Tetrahedron 2008,
64, 3047.
MS (EI, 70 eV, 30 °C): m/z (%) = 199 (100, [M+]), 152 (51), 141 (9), 127
(4), 115 (5), 69 (3).
HRMS (EI): m/z calcd for C12H9NO2: 199.0628; found: 199.0629.
2-(4-Nitrophenyl)naphthalene (3aa)
Pale yellow powder; yield: 0.164 g (66%); mp 133–135 °C (Lit.23p mp
134–139 °C).
(9) (a) Roglans, A.; Pla-Quintana, A.; Moreno-Mañas, M. Chem. Rev.
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Dhalluin, M.; Le Grognec, E.; Felpin, F. X. Org. Process Res. Dev.
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Chem 2010, 3, 502.
IR (ATR): 1928.8, 1590.6, 1509.4, 1392.9, 1336.4, 1195.9, 1146.3,
1130.6, 1105.9, 959.5, 902.3, 862.2, 848.6, 820.3, 758.1, 718.6, 695.1,
623.6, 536.5, 482.7, 471.0, 440.8, 424.2 cm–1
.
1H NMR (CDCl3, 300 MHz): δ = 8.36 (m, 2 H), 8.12 (s, 1 H), 8.02–7.85
(m, 5 H), 7.79–7.73 (m, 1 H), 7.61–7.53 (m, 2 H).
13C NMR (CDCl3, 75 MHz): δ = 133.4, 133.2, 129.0, 128.4, 128.0 (2 C),
127.7, 126.9, 126.8 (2 C), 124.9, 124.2 (2 C) (3 quaternary carbons
could not be observed).
MS (EI, 70 eV, 70 °C): m/z (%) = 249 (39, [M+]), 234 (14), 231 (23), 180
(26), 169 (53), 152 (22), 131 (24), 119 (34), 112 (10), 69 (100), 43 (8).
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Abrishami, F. Tetrahedron Lett. 2012, 53, 406.
HRMS (EI): m/z calcd for C16H11NO2: 249.0786; found: 249.0784.
(12) Cacchi, S.; Caponetti, E.; Casadei, M. A.; Di Giulio, A.; Fabrizi, G.;
Forte, G.; Goggiamani, A.; Moreno, S.; Paolicelli, P.; Petrucci, F.;
Prastaro, A.; Saladino, M. L. Green Chem. 2012, 14, 317.
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Roglans, A. Tetrahedron 2013, 69, 9761.
Acknowledgment
We acknowledge the DAAD and Russian Ministry of Education and
Science (Scientific Program No. 5.746.2016 ‘Mikhail Lomonosov’) and
the members of the group of the SFB TRR 88 (3MET) and the financial
support of 3MET. The work was further supported by the Helmholtz
program Biointerfaces in Technology and Medicine (N.J. and S.B.), and
the Compound’s Platform (ComPlat).
(14) Jadhav, S. N.; Kumbhar, A. S.; Rode, C. V.; Salunkhe, R. S. Green
Chem. 2016, 18, 1898.
(15) Filimonov, V. D.; Trusova, M.; Postnikov, P.; Krasnokutskaya, E.
A.; Lee, Y. M.; Hwang, H. Y.; Kim, H.; Chi, K. W. Org. Lett. 2008,
10, 3961.
(16) (a) Trusova, M. E.; Kutonova, K. V.; Kurtukov, V. V.; Filimonov, V.
D.; Postnikov, P. S. Res. Eff. Technol. 2016, 2, 36. (b) Moon, M. E.;
Choi, Y.; Lee, Y. M.; Vajpayee, V.; Trusova, M.; Filimonov, V. D.;
Chi, K.-W. Tetrahedron Lett. 2010, 51, 6769. (c) Lee, Y. M.; Moon,
M. E.; Vajpayee, V.; Filimonov, V. D.; Chi, K.-W. Tetrahedron
2010, 66, 7418. (d) Trusova, M. E.; Krasnokutskaya, E. A.;
Postnikov, P. S.; Choi, Y.; Chi, K.-W.; Filimonov, V. D. Synthesis
2011, 2154.
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0036-1588919.
S
u
p
p
ortioInfgrmoaitn
S
u
p
p
ortiInfogrmoaitn
(17) Kutonova, K. V.; Trusova, M. E.; Postnikov, P.; Filimonov, V. D.;
Parello, J. Synthesis 2013, 45, 2706.
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