Palladium catalyzed desulfinylative couplings between aryl sulfinates and aryl bromide/iodide for the synthesis of biaryls

Article abstract of DOI:10.1016/j.tet.2016.05.081

We have synthesized biaryls from the coupling reaction between aryl sulfinates and aryl halides using homogeneous palladium catalytic system. The developed method is simple and efficient. These methodologies are particularly useful to prepare symmetrical as well as unsymmetrical biaryls with excellent product yield. The suggested protocol demonstrated a broad substrate scope.

Full text of DOI:10.1016/j.tet.2016.05.081

Accepted Manuscript
Palladium catalyzed desulfinylative couplings between aryl sulfinates and aryl
bromide/iodide for the synthesis of biaryls
Sitaram Haribhau Gund, Kishor Eknath Balsane, Jayashree Milind Nagarkar
PII:
S0040-4020(16)30498-7
10.1016/j.tet.2016.05.081
TET 27808
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 March 2016
Revised Date: 30 May 2016
Accepted Date: 31 May 2016
Please cite this article as: Gund SH, Balsane KE, Nagarkar JM, Palladium catalyzed desulfinylative
couplings between aryl sulfinates and aryl bromide/iodide for the synthesis of biaryls, Tetrahedron
(2016), doi: 10.1016/j.tet.2016.05.081.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Palladium catalyzed desulfinylative
Leave this area blank for abstract info.
couplings between aryl sulfinates and aryl
bromide/iodide for the synthesis of biaryls
Sitaram Haribhau Gund, Kishor Eknath Balsane and Jayashree Milind Nagarkar*

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Palladium catalyzed desulfinylative couplings between aryl sulfinates and aryl
bromide/iodide for the synthesis of biaryls
Sitaram Haribhau Gund, Kishor Eknath Balsane and Jayashree Milind Nagarkar*
Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai – 400019, India
E-mail:jayashreenagarkar@yahoo.co.in, jm.nagarkar@ictmumbai.edu.in.
.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
We have synthesized biaryls from the coupling reaction between aryl sulfinates and aryl halides
using homogeneous palladium catalytic system. The developed method is simple and efficient.
These methodologies are particularly useful to prepare symmetrical as well as unsymmetrical
biaryls with excellent product yield. The suggested protocol demonstrated a broad substrate
scope.
Available online
2
016 Elsevier Ltd. All rights reserved.
Keywords:
Palladium
Cross-coupling
Aryl sulfinate
Aryl halides
Triphenyl phosphate
Introduction
Silver catalyzed C-C coupling of aryl halides with phenylboronic
7a
acid (Fig. 1, route a), Pd-NCs-catalyzed Migitae-Kosugie-Stille
Carbon-carbon (C-C) bond formation is one of the most
important reactions in organic synthesis due to its wide
applications in pharmaceuticals, biologically active compounds
and in advanced material. It is also an important tool in the
7b
cross-coupling reactions (Fig. 1, route b), palladium catalyzed
7c
C-C cross coupling reaction of tri-aryl bismuth with arylhalides
(
Fig. 1, route c) and Hiyama cross-coupling reaction of various
7d
aryl halides with triethoxy(phenyl)silane (Fig. 1, route d) are
well studied methods for the synthesis of biaryls.
1
synthesis of natural products. The most frequently employed
methods for the synthesis of unsymmetrical biphenyl derivatives
2
3
4
Arenesulfinates have been shown to be more reactive
are Suzuki, Stille and Hiyama cross-coupling reactions.
Palladium catalyzed cross coupling reactions form an important
class of carbon-carbon bond forming reactions. The catalytic
activity of Pd-based catalysts can be tuned by phosphine ligands
to get the higher stability in the reactions as well as prolonged
8
substrates for the synthesis of various aromatic compounds .
Recently, arenesulfinates were employed as electrophilic partners
9
for palladium catalyzed Hiyama type cross-coupling reactions.
Palladium catalysed desulfitative arylation of 3-haloquinolines
with arylsulfinates using additive tetrabutylammonium chloride
5
lifetimes. Palladium and its complexes have been employed as
10
6
is reported.
Pat Forgione and co-workers reported
efficient and active catalysts for the cross-coupling reactions. An
overview of some of the earlier reported methods for the
synthesis of symmetrical and unsymmetrical biaryls by using
transition metal-catalyzed homocoupling reactions are presented
desulfinylative palladium catalyzed cross-coupling of aryl
sulfinates with aryl bromides. High temperature and catalyst
loading, higher quantity of arenesulfinate and lower yield are the
11
(
Fig. 1).
shortcomings of this protocol. To the best of our knowledge, for
the first time, we are reporting the coupling reaction of aryl
iodide and sodium arylsulfinate. Sodium aryl sulfinate is
currently attracting much attention as it is easy to handle, stable
and can be conveniently prepared from the corresponding
inexpensive sulfonyl chloride. It is used as an ideal alternative
12
aryl source for the synthesis of biaryl compounds. Arylsulfinate
can be used in a palladium catalyzed desulfitative coupling
reactions, such as desulfitative C–P coupling of aryl sulfinate
13
metal salts and H-phosphonates, even though arenesulfinates
1
4
were employed in a desulfinative homocoupling reaction.
However, previous reported methods have some drawbacks such
as use of high reaction temperature, high catalyst loading and low
product yield. Apart from this, by-product formation due to
Fig. 1 Synthesis of biaryls by using metal catalyzed coupling
methods.

2
Tetrahedron Letters
ACCEPTED MANUSCRIPT
2
Results and discussion
a
Table 1. Optimization of reaction parameters.
b
Entry
Catalyst (mol%)
Ligand (mol%)
Base
Time (h)
Conversion
(%)
Yield(%)
(mmol)
3
4
1
2
3
4
.
.
.
.
Pd(dppf)Cl2 (2.5)
Pd(dppf)Cl2 (2.5)
Pd(dppf)Cl2 (2.5)
Pd(dppf)Cl2 (2.5)
P(OPh)3
P(OPh)3
P(OPh)3
P(OPh)3
(5)
(5)
(5)
(5)
NaHCO3
24
24
24
24
86
79
07
CS CO3
100
69
64
67
94
36
02
06
2
Na CO3
2
K CO3
2
100
5
6
.
.
Pd(OAc)2
PdCl2
(5)
(5)
P(OPh)3
P(OPh)3
(10)
(10)
K CO3
48
48
100
100
74
75
26
25
2
K CO3
2
7
8
9
.
.
.
Pd(PPh3)4
(2.5)
__
P(OPh)3
P(Ph)3
K CO3
24
24
24
24
24
42
39
66
95
53
42
39
64
90
51
00
00
02
05
02
2
Pd(PPh ) Cl (2.5)
(5)
(5)
K CO3
2
3
2
2
Pd(dppf)Cl2 (2.5)
Pd(dppf)Cl2 (2.5)
Pd(dppf)Cl2 (2.5)
K CO3
2
1
1
0.
1.
Tri(o-tolyl)phosphine
5)
K CO3
2
(
__
K CO3
2
1
1
2.
3.
Pd(OAc)2
PdCl2
(5)
(5)
Dppf
Dppf
(5)
(5)
K CO3
48
48
90
75
71
15
29
2
K CO3
2
100
1
1
1
4.
5.
6.
Pd(dppf)Cl2
(2)
P(OPh)3
P(OPh)3
P(OPh)3
(4)
(5)
(5)
K CO3
24
24
24
88
82
94
66
06
06
05
2
c
Pd(dppf)Cl2 (2.5)
Pd(dppf)Cl2 (2.5)
K CO3
2
100
71
d
K CO3
2
a
The reactions were performed by using 4-methoxy iodobenzene 1(0.5 mmol), sodium aryl sulfinates 2(0.75 mmol), Palladium source (mol%), ligand source
mol%), Base (1.5 mmol), DMF (2 mL), 150 °C, under N , GC yields based on 1, 160 °C, 140 °C.
2
b
c
d
(
P(OPh) as ligand in DMF at 150 °C under inert atmosphere
3
(
Scheme 1).
homocoupling is also observed in most of the above reported
methods, which is the main drawback. Eventually it also
decreases the yield of desired product. Hence a coupling reaction
between aryl halide and sodium arylsulfinate was highly
desirable which could overcome the above limitations. Herein,
we report the synthesis of biaryls using aryl halides and sodium
Scheme 1. Reaction between 4-methoxy iodobenzene and
sodium aryl sulfinate.
arylsulfinates as starting materials, Pd(dppf)Cl as catalyst and
2

3
The optimization studies were performed
A
onCCtheEPco
TED
ng MANUSCRIPT
up
li
reaction of 4-methoxy iodobenzene with sodium arylsulfinates.
Initially screening of various bases for desulfinylative coupling
was carried out by employing NaHCO , K CO , CS CO and
Cl
I
4
(3d) 88
(3e) 88
(3f) 87
(3g) 86
(3h) 87
(3c) 90
(3i) 91
(3j) 88
(3k) 87
(3l) 86
(3m) 86
(3n) 84
(3o) 85
3
2
3
2
3
Na CO (Table 1). In the course of this study, it was found that
2
3
K CO is the most effective base as it afforded maximum yield
2
3
(94 %) of the desired product (Table 1, entries 1-4). It was also
5
found that 1.5 mmol of K CO was sufficient for the reaction. We
2
3
also investigated suitable palladium source as a catalyst for
model reaction by employing Pd(dppf)Cl2, Pd(OAc) , PdCl ,
2
2
6
Pd(PPh ) and Pd(PPh ) Cl as catalyst (Table 1, entries 4-8). It
3
4
3 2
2
was observed that Pd(dppf)Cl was the best choice as it afforded
2
9
4% yield of biaryl with 100% conversion of aryl halide, while
I
Pd(OAc) , PdCl , Pd(PPh ) and Pd(PPh ) Cl were found to be
2
2
3 4
3 2
2
7
inferior. When the amount of catalyst Pd(dppf)Cl was decreased
2
CF3
from 2.5 mol% to 2.0 mol% the yield also decreased from 94% to
8
2% (Table 1, entry 14). Phosphine ligand plays a very crucial
role in homogeneous palladium catalysis with respect to product
yield. Therefore, we carried out the model reaction with
8
Pd(dppf)Cl as a catalyst in DMF using various ligands. Here we
2
screened three ligands such as triphenyl phosphite [P(OPh)3],
triphenyl phosphine [P(Ph) ] and Tri(o-tolyl)phosphine (Table 1,
3
9
entries 4, 9, 10). The results clearly show that triphenyl phosphite
is the most superior ligand than others giving maximum product
yield. Triphenyl phosphite is a better ligand than triphenyl
phosphine (Table 1, entries 4, 9). The phosphite ligand stabilizes
15
10
Pd(0) and prevent the formation of inactive palladium black.
Triphenyl phosphite is a stronger π-acceptor and a weaker ϭ-
16
donar than triphenyl phosphine. The selectivity is low in the
absence of ligands and only 51 % product yield was obtained
1
1
1
1
1
1
1
2
3
4
5
6
(
Table 1, entry 11).
We also performed model reactions with
Pd(OAc)2 and PdCl2 (5mol%) in presence of Dppf (1,1′-
bis(diphenylphosphino)ferrocene) ligand (5mol%) at 150 °C for
Cl
I
4
8h which afforded 75% and 71% yield of the product
respectively (Table 1, entries 12,13). The optimum temperature
was found to be 150 °C for the model reaction. Increase in
temperature to 160 °C, did not improve the product yield,
whereas significant decrease in the product yield was observed
when the temperature was decreased to 140 °C (Table 1, entries
4
, 15, 16). The reaction time was 24h for aryl iodides and 26h for
aryl bromide derivatives to achieve maximum conversions.
I
CF3
a
Table 2. Reaction between aryl iodides and aryl sulfinates.
a
Entry
Ar-X
Ar-SO
2
Na
Yield
The reactions were performed by using aryl iodides (0.5 mmol), aryl
sulfinates (0.75 mmol), Pd(dppf)Cl (2.5 mol%), P(OPh) (5 mol%), K CO
(1.5 mmol), DMF (2 mL), 150 °C, 24h under N . Isolated yield.
2
3
2
3
b
b
(%)
2
All above experiments reveal that the optimized reaction
conditions are 4-methoxy iodobenzene (0.5 mmol), sodium
arylsulfinates (0.75 mmol), Pd(dppf)Cl (2.5 mol%), P(OPh) (5
2
3
1
2
3
(3a) 91
(3b) 92
(3c) 90
mol%), K CO (1.5 mmol), DMF (2 mL), 150 °C temperature
2
3
and 24h reaction time under inert atmosphere. To examine the
scope of this desulfinylative cross-coupling reaction, we have
investigated the reactions using a variety of aryl iodides and aryl
sulfinates as substrates under the optimized reaction conditions.
The results are shown in Table 2. Aryl iodides with many
valuable functional groups present on aromatic ring such as -
OCH , -Cl, -F, -CH , -CF and -CN were well tolerated to give
3
3
3

4
Tetrahedron
le MANUSCRIPT
the desired unsymmetrical biaryl in good to
A
hig
C
h
C
yie
E
ld
P
s
T
(T
E
ab
D
2
, entries 1–16). Regardless of their electronic characters, aryl
1
1
1
1
2
3
(3q)82
(3r)78
(3s)81
sulfinates coupled smoothly with aryl iodides bearing both
electron-deficient and electron-rich substituents, to afford the
corresponding products in good to excellent yields. It was also
observed that the yield was lower in the case of ortho substituted
aryl halides than those obtained with the para substituted ones,
which might be due to steric factors.
a
Table 3. Reaction between aryl bromides and aryl sulfinates.
Entry
Ar-X
Ar-SO Na
Yield
b
2
a
The reactions were performed by using aryl bromides (0.5 mmol), aryl
sulfinates (0.75 mmol), Pd(dppf)Cl (2.5 mol%), P(OPh) (5 mol%), K CO
1.5 mmol), DMF (2 mL), 150 °C, 26h under N . Isolated yield.
(
%)
2
3
2
3
b
(
2
1
(3a)90
(3b)91
(3e)87
(3c)89
(3h)87
(3c)89
(3i)90
(3l)87
(3j)89
In order to investigate the scope of aryl halides in the coupling
with aryl sulfinates, different aryl bromides were employed in the
reaction (Table 3, entries1-13). Electron donating and electron-
withdrawing aryl bromides readily coupled to give good yields of
respective unsymmetrical biaryl products. A trace amount of
biphenyl was detected as a by-product in the reactions of aryl
iodides and aryl bromides.
2
3
4
5
6
7
8
9
Table 4. Reaction between various aryl halides and aryl
a
sulfinates.
Entry
Ar-X
Ar-SO
2
Na
Yield
b
(%)
1
2
3
4
5
(3P) 79
(3t)80
(3t)78
(3u)81
Br
S
(3v)84
6
(3a)00
a
The reactions were performed by using aryl bromides (0.5 mmol), aryl
sulfinates (0.75 mmol), Pd(dppf)Cl
2
(2.5 mol%), P(OPh)
3
(5 mol%), K
2
CO
3
b
(1.5 mmol), DMF (2 mL), 150 °C, 26h under N
2
. Isolated yield.
1
0
(3o)85
Additionally, the reaction was carried out quite efficiently when
the scope of this catalytic system was further extended to the
coupling of heteroaryl halides with aryl sulfinates to yield biaryls

5
1
3
(
Table 4, entries1-5). However, no product w
A
a
C
s f
C
or
E
m
P
ed
T
w
E
h
D
en MA4.
N
2 H
U
z
S
, 1
C
H
R
),
I
7.28 (d, J = 7.8 Hz, 2H), 2.42 (s, 3H). C NMR
P
T
chlorobenzene was used in the coupling with sodium
benzenesulfinate under optimized reaction conditions (Table 4,
entry 6). The mechanism (Scheme 1) is consistent with the one
(101 MHz, CDCl ) δ 141.17, 138.36, 137.00, 129.47, 128.70,
126.99, 126.97, 21.10. GCMS (m/z/rel.int.): 168(M ): 82(12.5),
3
+
152(26.0), 165(26.7), 167(69.0), 168(100).
11
proposed by Pat Forgione and co-workers.
17a
3
-chloro-1, 1’-biphenyl (3d). (83.0 mg, 88%) as a yellow
1
Conclusions
liquid. H NMR (400 MHz, CDCl ) δ 7.56 (dd, J = 8.4, 1.0 Hz,
3
13
3
H), 7.49 – 7.41 (m, 3H), 7.40 – 7.28 (m, 3H). C NMR (101
In conclusion, we have developed a simple and efficient method
for the desulfinylative cross-coupling reaction between aryl
sulfinates and aryl halides. Controlling the extent of
homocoupling of aryl halide and increasing the yield of desired
MHz, CDCl ) δ 143.03, 139.77, 134.60, 129.96, 128.87, 127.84,
3
+
1
6
27.26, 127.19, 127.09, 125.28. GCMS (m/z/rel.int.): 188(M ):
3(9.0), 76(23.5), 152(48.7), 153(28.4), 188(100).
17a
product efficiently by the catalyst Pd(dppf)Cl is the highlight of
4-fluoro-1, 1’-biphenyl (3e). (76.0 mg, 88%) as a white solid.
H NMR (400 MHz, CDCl ) δ 7.54 (qd, J = 5.1, 3.0 Hz, 4H),
7.43 (dd, J = 10.3, 4.8 Hz, 2H), 7.38 – 7.30 (m, 1H), 7.17 – 7.07
(m, 2H). C NMR (101 MHz, CDCl ) δ 163.66, 161.21, 140.23,
137.30, 128.88 – 128.51, 127.22, 126.98, 115.68, 115.46. GCMS
(m/z/rel.int.): 172(M ): 63(3.1), 73(5.3), 85(12.2), 171(38.2),
2
1
this protocol. The developed methodology tolerates wide range
of electron donating, electron withdrawing and sterically
hindered functional groups and afforded the respective biphenyls
with low palladium loadings. Coupling product afforded by less
reactive aryl bromide is the advantage of this method.
3
1
3
3
+
1
72(100).
Experimental Section
General
17b
2
-methyl-1, 1’-biphenyl (3f). (74.0 mg, 87%) as a colourless
1
liquid. H NMR (400 MHz, CDCl ) δ 7.44 (ddd, J = 7.6, 2.8, 0.9
3
The Palladium catalysts were purchased from Sigma-Aldrich. All
chemicals were purchased from Sigma Aldrich, Alfa Asear and
commercial suppliers. The resulting products were purified by
column chromatography on silica gel (100-200 mesh; petroleum
ether). The reaction was monitored by TLC and GC analysis
performed on PerkinElmer Clarus 480. GC equipped with flame
ionized detector with capillary column (Elite- 1701, 30m X 0.32
Hz, 2H), 7.37 (ddd, J = 6.2, 2.3, 0.9 Hz, 3H), 7.32 – 7.25 (m,
13
4H), 2.31 (s, 3H). C NMR (101 MHz, CDCl ) δ 141.96, 135.33,
3
130.30, 129.79, 129.19, 128.06, 127.24, 126.75, 125.75, 20.46.
+
GCMS (m/z/rel.int.): 168(M ): 63(7.9), 82(21.8), 153(49.3),
165(40.9), 168(100).
17c
2
-(trifluoromethyl)-1, 1’-biphenyl (3g). (96.0 mg, 86%) as a
1
yellow liquid. H NMR (400 MHz, CDCl ) δ 7.74 (d, J = 7.5 Hz,
3
X 0.25) using N as carrier gas. GC-MS (Shimadzu QP 2010)
2
1
H), 7.55 (t, J = 7.5 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.41 – 7.36
instrument with EI detector and capillary column (Elite – 1, 30m,
13
1
(m, 3H), 7.32 (dd, J = 5.9, 3.5 Hz, 3H). C NMR (101 MHz,
CDCl ) δ 141.38, 139.80, 131.99, 131.24, 128.91, 127.63,
1
7
0
.32mm ID, 0.25 ꢀm film thickness) using helium carrier gas. H
13
3
and C NMR spectra were recorded with 400 MHz and 101
MHz spectrometer.
+
27.28, 126.00, 125.47, 122.75. GCMS (m/z/rel.int.): 222(M ):
6(5.1), 100(6.0), 152(13.9), 201(35.1), 222(100).
Desulfinylative palladium-catalyzed cross-coupling of aryl
sulfinates with aryl halides; General procedure
17a
1
, 1’-biphenyl]-4-carbonitrile (3h). (78.0 mg, 87%) as a white
1
solid. H NMR (400 MHz, CDCl ) δ 7.74 – 7.64 (m, 4H), 7.58
3
A mixture of aryl halides (0.5 mmol), aryl sulfinates (0.75
mmol), Pd(dppf)Cl (2.5 mol%), P(OPh) (5 mol%), K CO (1.5
mmol) and 2 mL of DMF in a schlenk tube was heated to 150 °C
under inert atmosphere (24h for aryl iodides and 26h for aryl
bromides). The reaction mixture was cooled to room temperature,
diluted with ethyl acetate and filtered through a plug of Celite.
(dd, J = 5.2, 3.3 Hz, 2H), 7.50 – 7.44 (m, 2H), 7.44 – 7.38 (m,
13
1H). C NMR (101 MHz, CDCl ) δ 145.64, 139.14, 132.55,
2
3
2
3
3
129.07, 128.62, 127.70, 127.19, 118.89, 110.89. GCMS
+
(m/z/rel.int.): 179(M ): 63(5.0), 76(11.8), 151(15.9), 178(26.8),
179(100).
17d
4
-methoxy-4'-methyl-1, 1’-biphenyl (3i). (91.0 mg, 91%) as a
The filtrate was washed sequentially with H O and brine. The
1
2
white solid. H NMR (400 MHz, CDCl ) δ 7.54 – 7.48 (m, 2H),
3
organic layer was separated, dried (Na SO ), and concentrated
2
4
7
2
.45 (d, J = 8.1 Hz, 2H), 7.27 – 7.22 (m, 2H), 7.00 – 6.94 (m,
under vacuum. The crude product was purified by column
chromatography (silica gel; petroleum ether). All the products
13
H), 3.84 (s, 3H), 2.38 (s, 3H). C NMR (101 MHz, CDCl ) δ
3
1
13
158.88, 137.92, 136.34, 133.70, 133.02, 129.42, 127.93, 126.56,
were analyzed by GC-MS. H NMR, C NMR and IR of only
representative products are given, as all the products are highly
reported.
+
1
1
14.12, 55.32, 21.06. GCMS (m/z/rel.int.): 198(M ): 99(6.8),
28(9.0), 155(34.6), 183(54.4), 198(100).
17d
17a
1
4, 4’-dimethyl-1, 1’-biphenyl (3j). (81.0 mg, 88%) as a white
Biphenyl (3a). (71.0 mg, 91%) as a white solid. H NMR (400
1
solid. H NMR (400 MHz, CDCl ) δ 7.49 (d, J = 8.1 Hz, 4H),
3
MHz, CDCl ) δ 7.65 – 7.57 (m, 4H), 7.45 (dd, J = 10.3, 4.8 Hz,
13
3
13
7.24 (d, J = 7.9 Hz, 4H), 2.39 (s, 6H). C NMR (101 MHz,
4
1
7
H), 7.40 – 7.31 (m, 2H). C NMR (101 MHz, CDCl ) δ 141.21,
28.74, 127.24, 127.16. GCMS (m/z/rel.int.): 154(M ): 51(7.7),
6(22.2), 152(28.8), 153(42.3), 154(100).
3
+
CDCl
3
) δ 138.25, 136.68, 129.42, 126.79, 21.09. GCMS
+
(m/z/rel.int.): 182(M ): 51(2.5), 89(13.5), 152(11.4), 167(48.8),
1
82(100).
1
7a
4
-methoxy-1, 1’-biphenyl (3b). (85.0 mg, 92%) as a white
17e
1
3-chloro-4'-methyl-1, 1’-biphenyl (3k). (88.0 mg, 87%) as a
solid. H NMR (400 MHz, CDCl ) δ 7.57 – 7.50 (m, 4H), 7.44 –
1
3
colourless liquid. H NMR (400 MHz, CDCl ) δ 7.56 – 7.53 (m,
3
7
3
1
.37 (m, 2H), 7.33 – 7.26 (m, 1H), 7.01 – 6.94 (m, 2H), 3.84 (s,
13
1H), 7.48 – 7.41 (m, 3H), 7.37 – 7.33 (m, 1H), 7.32 – 7.28 (m,
H). C NMR (101 MHz, CDCl ) δ 159.10, 140.79, 133.76,
13
3
1
H), 7.28 – 7.24 (m, 2H), 2.39 (s, 3H). C NMR (101 MHz,
28.68, 128.12, 126.70, 126.62, 114.17, 55.32. GCMS
+
CDCl
3
) δ 142.95, 137.72, 136.87, 134.55, 129.9, 129.59, 127.13,
(m/z/rel.int.): 184(M ): 63(5.8), 115(35.4), 141(56.8), 169(51.2),
+
1
1
26.80, 125.06, 21.12. GCMS (m/z/rel.int.): 202(M ): 81(25.8),
52(25.1), 166(21.5), 167(55.6), 202(100).
1
84(100).
1
7a
4
-methyl-1, 1’-biphenyl (3c). (76.0 mg, 90%) as a white solid.
17e
1
4-fluoro-4'-methyl-1, 1’-biphenyl (3l). (80.0 mg, 86%) as a
H NMR (400 MHz, CDCl ) δ 7.63 – 7.58 (m, 2H), 7.52 (d, J =
1
3
white solid. H NMR (400 MHz, CDCl ) δ 7.56 – 7.50 (m, 2H),
3
8
.1 Hz, 2H), 7.45 (dd, J = 10.4, 4.8 Hz, 2H), 7.34 (dd, J = 10.4,
7
.47 – 7.42 (m, 2H), 7.25 (d, J = 7.8 Hz, 2H), 7.17 – 7.08 (m,

6
Tetrahedron
1
3
+
2
H), 2.40 (s, 3H). C NMR (101 MHz, C
A
D
C
C
C
l )
E
δ
P
1
T
63
E
.4
D
9, MA11
NU
5.
151(9.0),
1
78
S
.
C
GC
R
M
IP
S (m/z/rel.int.): 205(M ): 77(11.0), 102(17.0),
T
3
-
1
2
1
61.05, 137.46, 137.13, 137.02, 129.53, 126.84, 115.64, 115.43,
1.08. GCMS (m/z/rel.int.): 186(M ): 82(9.7), 91(11.0),
65(30.0), 168(30.9), 186(100).
176(19.0),
205(100).
IR(ATR)
ν(cm
+
)3058,2926,1592,1502,1468,1387,1238,957,807,756,697,569.
Acknowledgment
17f
2
, 4’-dimethyl-1, 1’-biphenyl (3m). (79.0 mg, 86%) as a yellow
1
The author S. H. Gund is greatly thankful to the university grant
commission, India for providing financial support under UGC-
SAP-SRF program.
liquid. H NMR (400 MHz, CDCl ) δ 7.29 – 7.21 (m, 8H), 2.41
3
1
3
(s, 3H), 2.29 (s, 3H). C NMR (101 MHz, CDCl ) δ 141.83,
3
1
1
1
38.99, 136.36, 135.38, 130.27, 129.84, 129.06, 128.76, 127.05,
25.73, 21.18, 20.53. GCMS (m/z/rel.int.): 182(M ): 82(12.6),
15(11.8), 152(24.4), 167(100), 182(82.8).
+
References and notes
1
.
(a) Wolf, C.; Kovi, K. E. Eur. J. Org. Chem. 2006, 1917. (b)
Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J.
Am. Chem. Soc. 2005, 127, 4685. (c) Zhang, X. Q.; Qiu, Y. P.;
Rao, B.; Luo, M. M. Organometallics 2009, 28, 3093. (d)
Karthikeyan, T.; Sankararaman, S. Tetrahedron 2009, 50, 5834.
1
7g
4
'-methyl-2-(trifluoromethyl)-1, 1’-biphenyl (3n).
(100 mg,
1
8
4%) as a colourless liquid. H NMR (400 MHz, CDCl ) δ 7.72
3
(d, J = 7.9 Hz, 1H), 7.53 (t, J = 7.7 Hz, 1H), 7.43 (t, J = 7.9 Hz,
13
1
H), 7.31 (d, J = 7.6 Hz, 1H), 7.21 (m, 4H), 2.40 (s, 3H).
C
(
e) Li, F. W.; Bai, S. Q.; Andy Hor, T. S. Organometallics 2008,
NMR (101 MHz, CDCl ) δ 137.28, 136.98, 136.78, 132.12,
3
27, 672. (f) Patil, S. A.; Weng, C. M.; Huang P. C.; Hong, F. E.
Tetrahedron 2009, 65, 2889. (g) Fang, Y.; Karisch R.; Lautens, M.
J. Org. Chem. 2007, 72, 1341.
1
31.21, 128.78, 128.42, 127.09, 125.98, 21.21. GCMS
+
(m/z/rel.int.): 236(M ): 117(13.0), 167(27.9), 196(14.0),
2
01(17.5), 236(100).
2
3
.
.
(a) Miyaura N.; Suzuki, A. Chem. Rev. 1995, 95, 2457. (b) Yokoi,
H.; Hiraoka, Y.; Hiroto, S.; Sakamaki, D.; Seki, S.; Shinokubo, H.
nature communications 6:8215. (c) Sharma, K.; Kumar, M.;
Bhalla, V. Chem. Commun. 2015, 51, 12529. (d) Wu, G.; Han, F.;
Zhao, Y. RSC Adv. 2015, 5, 69776. (e) Boruah, P.; Ali, A.;
Chetia, M.; Saikia B.; Sarma, D. Chem. Commun. 2015, 51,
11489.
17h
4
'-methyl-[1, 1’-biphenyl]-4-carbonitrile (3o). (100 mg, 84%)
1
as a colourless liquid. H NMR (400 MHz, CDCl ) δ 7.72 – 7.62
3
(m, 4H), 7.48 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 2.40
13
(s, 3H). C NMR (101 MHz, CDCl ) δ 145.56, 138.72, 136.22,
3
1
32.54, 129.81, 127.43, 127.03, 119.04, 110.47, 21.18. GCMS
+
(m/z/rel.int.): 193(M ): 83(3.5), 95(10.1), 165(19.7), 192(45.4),
(a) Milstein D.; Stille, J. K. J. Am. Chem. Soc. 1979, 101, 4992.
1
93(100).
(b) Kratochvil, J.; Novak, Z.; Ghavre, M.; Novakova, L.; zicka,
7
-(tert-butyl)-5-phenyl-7H-pyrrolo [2, 3-d]pyrimidine (3p). (100
A.; Kunes, J.; Pour, M. Org. Lett. 2015, 17, 520. (c) Maeda, C.;
Taniguchi, T.; Ogawa, K.; Ema, T. Angew. Chem. Int. Ed. 2015,
1
mg, 79%) as a white solid. H NMR (400 MHz, CDCl ) δ 9.23 (s,
1
7
3
5
4, 134. (d) Liu, H.; Wu, F.; Zhao, B.; Meng, L.; Wang, G.;
H), 8.87 (d, J = 15.2 Hz, 1H), 7.62 – 7.56 (m, 2H), 7.53 (s, 1H),
Zhang, J.; Shen, P.; Tan, S. Dyes and Pigments 2015, 120, 44.
13
.44 (t, J = 7.6 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H), 1.83 (s, 9H).
C
NMR (101 MHz, CDCl ) δ 151.07, 149.64, 148.05, 148.03,
4.
(a) Zhang, L.; Wu, J. J. Am. Chem. Soc. 2008, 130, 12250. (b)
Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1988, 53, 918. (c)
Traficante, C.; Mata, E.; Delpiccolo, C. RSC Adv. 2015, 5, 26796.
3
1
33.51, 129.10, 126.97, 126.81, 123.99, 114.58, 57.60, 29.22.
+
GCMS (m/z/rel.int.): 251(M ): 115(4.6), 140(11.0), 168(5.4),
-
1
95(100),
251(16.9).
IR(ATR)ν(cm
5
.
Fleckenstein, C. A.; Plenio, H. Chem. Soc. Rev. 2010, 39, 694.
1
)3045,2973,2870,1587,1538,1460,1426,1370,1328,1204,944,75
2
,692,616,548,501.
6.
(a) Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 2002, 58,
9
6
633. (b) Alonso, F.; Beletskaya, I. P.; Yus, M. Tetrahedron 2008,
4, 3047.
1
7i
2
-(p-tolyl) naphthalene (3q). m. p. 93-95 °C, (90.0 mg, 82%) as
+
a white solid. GCMS (m/z/rel.int.): 218(M ): 94(12.2), 107(13.5),
1
7
.
(a) Das, R.; Chakraborty, D. Tetrahedron Lett. 2012, 53, 7023. (b)
Yano, H.; Nakajima, Y.; Yasushi Obora, Journal of
Organometallic Chem. 2013, 745, 258. (c) Chaudhari, K. R.;
Wadawale, A. P.; Jain, V. K. Journal of Organometallic Chem.
08(12.4), 217(34.2), 218(100).
17j
9
-(p-tolyl) anthracene (3r). m. p. 107-110 °C, (105 mg, 78%)
+
as a yellow solid. GCMS (m/z/rel.int.): 268(M ): 113(11.5),
1
2
012, 698, 15. (d) Hajipoura, A. R.; Rafieec, F.; Najafia, N. Appl.
26(26.7), 252(46.3), 253(38.0), 268(100).
Organometal. Chem. 2014, 28, 217.
17k
9
-(p-tolyl)phenanthrene (3s). m. p. 78-80 °C, (109 mg, 81%)
+
8. (a) Behrends, M.; Savmarker, J.; Sjoberg, P. J. R.; Larhed, M.
ACS Catal. 2011, 1, 1455. (b) Liu, J.; Zhou, X.; Rao, H.; Xiao, F.;
Li, C.; Deng, G. Chem. Eur. J. 2011, 17, 7996. (c) Rao, H.; Yang,
L.; Shuai, Q.; Li, C. Adv. Synth. Catal. 2011, 353, 1701. (d) Zhou,
C.; Liu, Q.; Li, Y.; Zhang, R.; Fu; X.; Duan, C. J. Org. Chem.
2012, 77, 10468. (e) Gund, S.; Shelkar, R.; Nagarkar, J. RSC Adv.
2015, 5, 62926. (f) Behrends, M.; Sävmarker, J.; Sjöberg, P. J. R.;
Larhed, M. ACS Catal. 2011, 1, 1455. (g) Miao, T.; Wang, G. –W.
Chem. Commun. 2011, 47, 9501. (h) Chen, J.; Li, J.; Su, W. Org.
Biomol. Chem. 2014, 12, 4078. (i) Zhao, F.; Tan, Q.; Xiao, F.;
Zhang, S.; Deng, G. –J. Org. Lett. 2013, 15, 1520. (j) Liu, J.;
Zhou, X.; Rao, H.; Xiao, F.; Li, C. –J.; Deng, G. –J. Chem. Eur. J.
2011, 17, 7996. (k) Skillinghaug, B.; Sköld, C.; Rydfjord, J.;
Svensson, F.; Behrends, M.; Sävmarker, J.; Sjöberg, P. J. R.;
Larhed, M. J. Org. Chem. 2014, 79, 12018. (l) Liu, S.; Chen, J.;
Zhang, R.; Zhao, F.; Deng, G. –J. Asian J. Org. Chem. 2014, 3,
as a white solid. GCMS (m/z/rel.int.): 268(M ): 126(24.7),
1
32(14.3), 252(41.5), 253(36.63), 268(100).
1
7l
1
2
-phenylthiophene (3t). (63.0 mg, 78%) as a white solid. H
NMR (400 MHz, CDCl ) δ 7.62 (dd, J = 7.8, 7.2 Hz, 2H), 7.50 –
7
δ 144.42, 134.39, 128.88, 128.01, 127.46, 127.17, 125.95,
1
3
13
.16 (m, 5H), 7.13 – 6.99 (m, 1H). C NMR (101 MHz, CDCl3)
+
24.80, 123.07. GCMS (m/z/rel.int.): 160(M ): 45(6.0), 77(7.0),
-
8
9(8.0),
115(38.0),
160(100).
IR(ATR)
ν(cm
1
)
3066,2921,2849,1600,1489,1447,1255,1204,1029,825,756,692.
1
7m
3
-phenylpyridine (3u). (63.0 mg, 81%) as a colourless liquid.
+
GCMS (m/z/rel.int.): 155(M ): 51(10.0), 77(7.0), 102(11.0),
1
27(16.0), 155(100).
1
2
150. (m) Bal Raju, K.; Mari, V.; Nagaiah, K. Synthesis 2013, 45,
867. (n) Ortgies,D. H.; Hassanpour, A.; Chen, F.; Woo, S.;
1
7n
1
5
-phenylquinoline (3v). (87.0 mg, 84%) as a yellow solid. H
NMR (400 MHz, cdcl ) δ 8.90 (d, J = 2.5 Hz, 1H), 8.22 (dt, J =
Forgione. P. Eur. J. Org. Chem. 2016, 408.
3
1
6
8.1, 8.8 Hz, 2H), 7.73 (t, J = 7.8 Hz, 1H), 7.55 – 7.31 (m, 6H),
.88 (ddd, J = 27.1, 7.9, 4.5 Hz, 1H). C NMR (101 MHz,
13
9. Cheng, K.; Hu, S.; Zhao, B.; Zhang, X.; Qi, C. J. Org. Chem.
2
013, 78, 5022.
CDCl ) δ 157.51, 149.69, 147.82, 140.57, 139.10, 136.76,
3
1
35.09, 129.99, 129.40, 128.30, 127.60, 126.79, 121.13, 119.47,
1
0. Colomb, J.; Billard,T. Tetrahedron Lett. 2013, 1471.

7
1
457.
ACCEPTED MANUSCRIPT
1
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Lapkowski, M.; Baj, S.; Grabarczyk, D. Cat. Comm. 2007, 8,