A simple, quick and novel protocol for biaryl synthesis using LiCl-promoted in situ-generated Pd nanoparticles

Article abstract of DOI:10.1002/aoc.4009

This paper describes a simple and a very quick protocol for biaryl synthesis using the Suzuki–Miyaura cross-coupling reaction. A quintessential role of salting-out agent LiCl was observed in the Suzuki–Miyaura cross-coupling reaction that enhanced the red

Full text of DOI:10.1002/aoc.4009

Received: 15 June 2017
DOI: 10.1002/aoc.4009
Revised: 2 July 2017
Accepted: 4 July 2017
C O M M U N I C A T I O N
A simple, quick and novel protocol for biaryl synthesis using
LiCl‐promoted in situ‐generated Pd nanoparticles
Parmita Phukan1 | Preeti Rekha Boruah1 | Praveen Singh Gehlot2 | Arvind Kumar2 |
Diganta Sarma1
1 Department of Chemistry, Dibrugarh
Abstract
University, Dibrugarh 786004 Assam,
This paper describes a simple and a very quick protocol for biaryl synthesis
using the Suzuki–Miyaura cross‐coupling reaction. A quintessential role of salt-
ing‐out agent LiCl was observed in the Suzuki–Miyaura cross‐coupling reaction
that enhanced the reduction rate of Pd (II) to a considerable extent, resulting in
the formation of nanosized palladium in a few seconds. The isolated Pd nano-
particles were characterized with X‐ray diffraction, dynamic light scattering,
TGA, transmission electron microscopy and scanning electron microscopy‐
dispersive X‐ray spectroscopy. The Suzuki–Miyaura cross‐coupling reaction
proceeded very well with the in situ‐generated Pd nanocatalysts furnishing
the desired biaryl adducts with excellent yields.
India
2 Academy of Scientific and Innovative
Research (AcSIR)‐Central Salt and Marine
Chemicals Research Institute, Council of
Scientific and Industrial Research (CSIR),
G. B. Marg, Bhavnagar 364002 Gujarat,
India
Correspondence
D. Sarma, Department of Chemistry,
Dibrugarh University, Dibrugarh 786004,
Assam, India.
Email: dsarma22@gmail.com
KEYWORDS
green chemistry, LiCl, nanoparticles, palladium chloride, Suzuki–Miyaura reaction
1 | INTRODUCTION
oxidation of hydrocarbons in automobiles,[8,9] carbon–
carbon bond‐forming reactions,[10] such as Heck,[11]
Nanoparticles of noble metals have received great atten-
tion in recent years because of their wide applications in
various fields, as well as their considerable structural sta-
bility. Nanostructured transition metal particles have
characteristic properties that are strikingly different from
those of the bulk, as a result of which they have gained
attention from both fundamental and technological
points of view.[1,2] Palladium, being one of the most versa-
tile metals, has been extensively used in the area of palla-
dium nanoparticle catalysis. Among the diverse metal
nanoparticles, palladium nanoparticles are of particular
interest in the field of nanocatalysis owing to their unique
properties and wide potential in a variety of organic reac-
tions and transformations,[3] including their applications
in the field of medicine, material science, sensor design
applications, etc. Nanosized palladium crystals act as
strong and efficient catalysts for a large number of impor-
tant catalytic reactions, such as hydrogenation reac-
tions,[4] electrochemical reductions and oxidations,[5–7]
Suzuki,[12] and Stille,[13] along with C‐N coupling reac-
tions.[14] Synthetic methodologies have been reported in
recent years, regarding the preparation of stable palla-
dium nanoparticles that can be used as catalysts. In gen-
eral, nanostructured catalysts are prepared chemically by
the reduction of Pd (II) salts using various reducing
agents. It has been observed that the methodologies
adopted during the synthesis of palladium nanoparticle
catalysts usually employ high‐performance technologies,
such as sonochemical method,[15] sonoelectrochemical
method,[16] microemulsion technique,[17] γ‐irradiation,[18]
UV‐irradiation,[19] polyol reduction,[20] etc. Moreover, the
methods adopted are usually facile, cost‐effective, but also
employ harsh reaction conditions that are both economi-
cally and environmentally hazardous. Apart from these,
the procedures employed are quite time‐consuming and
laborious. Herein, we report a simple as well as very quick
and efficient novel protocol for the synthesis of
biaryls using the salting‐out agent LiCl‐promoted in
Appl Organometal Chem. 2017;e4009.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 7
https://doi.org/10.1002/aoc.4009

2 of 7
PHUKAN ET AL.
situ‐generated palladium nanoparticle catalyst. The in
situ‐generated catalyst showed significant applicability in
Suzuki–Miyaura cross‐coupling reactions with satisfac-
tory yields of the desired coupled products. To the best
of our knowledge, this method is one of the quickest
methods that affords palladium nanoparticles within just
a few seconds.
in the catalyst loading to 0.5 mol% resulted in good iso-
lated yield of 89% (Table 1, entry 6). Further reactions
were carried out using 2 mol% of the catalyst, which was
established as the ideal optimized reaction condition for
catalyst loading.
In order to investigate the role of solvent and base, the
Suzuki reaction between 4‐bromoanisole and phenyl
boronic acid was performed. The choice of solvent and
base is a very important factor in carrying out Suzuki–
Miyaura cross‐coupling reactions. The reaction was
carried out in various organic and aqueous solvents, and
a significant variation in the yield of the coupled product
was noticed in each case. It was seen from Table 2 that
excellent yields of the desired coupled products were
obtained in water–i‐PrOH system (Table 2, entry 3). This
may be due to the greater solubility of the aryl halides in
i‐PrOH that increases the rate of reaction to a consider-
able extent. Literature reports indicate that base plays a
crucial role in Suzuki–Miyaura cross‐coupling reactions.
Hence, a variety of bases were also investigated to study
the reaction rate, and the best result was obtained using
K2CO3 as base and water–i‐PrOH as the solvent system
affording 96% of the desired product in just 30 min
(Table 2, entry 3). Use of a strong base enhances side‐
products, which in return decreases the yield of the
desired product, while a weak base fails to activate the
boronic acid for coupling. Because of these reasons, bases
such as KOH, Et3N, etc. do not give satisfactory results.
To explore the substrate scope and wide applications of
Suzuki–Miyaura cross‐coupling reactions, a series of aryl
bromides were allowed to react with aryl boronic acids
under the experimentally adopted optimized reaction con-
ditions (Table 3, entries 1–14). Both structurally as well as
electronically diverse substrates were tested using our
newly prepared palladium nanocatalysts in i‐PrOH:H2O
system at room temperature. It is noteworthy that the
catalytic system so prepared tolerated a large number of
functional groups, such as ―CH3, ―OCH3, ―CN,
―CHO, ―NO2, etc., and also afforded a quite significant
yield of the desired biaryls. Interestingly, heteroaryls such
as 3‐bromothiophene and 2‐bromopyridine also provided
us with good to excellent yield of the desired coupled prod-
uct (Table 3, entries 12, 13). Moreover, an important obser-
vation is that the formation of homocoupling product of
arylboronic acid, which sometimes lowers the expected
yield of the desired product, is not observed during our
experiment. Thus, this catalytic system affords a quite easy
and efficient method for the preparation of biaryls at room
temperature in a very short period of time.
2 | EXPERIMENTAL
2.1 | General reaction procedure for
Suzuki–Miyaura cross‐coupling reaction
The Suzuki–Miyaura cross‐coupling reaction was per-
formed using the in situ‐prepared palladium nanocatalyst.
A mixture of aryl bromide (1 mmol) and arylboronic acid
(1.2 mmol) was stirred in a 100‐ml round‐bottom flask in
isopropanol and water system (1 ml) with K2CO3 (2 mmol)
as base, PdCl2 as catalyst and 1 ml of 3 M LiCl (aq.) as pro-
moter. The reaction mixture was stirred for the indicated
time at room temperature. After completion of the reaction
(by thin‐layer chromatography monitoring), the reaction
mixture was extracted with diethyl ether (4 × 10 ml) and
after that the organic layer was washed with deionized
water (3 × 10 ml). The organic layer was then dried over
anhydrous Na2SO4, and the separated organic layer was
evaporated in a rotary evaporator. The products were
purified by column chromatography over silica gel using
n‐hexane and ethyl acetate (9:1 v/v) as eluents to obtain
the purified cross‐coupled product. The products were
then characterized by 1H NMR and 13C NMR.
3 | RESULTS AND DISCUSSION
To evaluate the efficiency of the catalytic system,
the Suzuki–Miyaura cross‐coupling reaction of
4‐bromoanisole and phenyl boronic acid was examined
in i‐PrOH and water system using K2CO3 as base at room
temperature (Table 1, entries 1–6). To adopt a satisfactory
optimized condition, the effect of the amount of PdCl2 in
the reaction was investigated. From Table 1, it has been
observed that excellent yield of the desired biaryl was
obtained within 30 min in the presence of 4 mol% of cat-
alyst (Table 1, entry 1). Decreasing the catalyst loading
to 3.5 mol% and 3 mol% afforded the coupled product in
sufficient isolated yield (Table 1, entries 2 and 3). A fur-
ther decrease in the catalyst loading to 2 mol% also
furnished the desired product with excellent yield within
a very short period of time (Table 1, entry 4). However,
a slight decrease in the yield was observed along with a
longer reaction time when the amount of catalyst was
decreased to 1 mol% (Table 1, entry 5). A further decrease
The effect of salting‐out agents such as LiCl on kinet-
ics of organic transformations has been discussed in terms
of several parameters, such as hydrophobic packing, sol-
vent pressure, hydrogen bonding, hydrophobic hydration,

PHUKAN ET AL.
3 of 7
TABLE 1 Effect of the catalyst quantity in the coupling reaction of 4‐bromoanisole and phenyl boronic acid in i‐PrOH/H2O as solvent,
K2CO3 as base and 3 M LiCl as promoter at room temperaturea
Entry
Catalyst (mol%)
Time (min)
Yieldb (%)
1
4
30
99
2
3
4
5
6
3.5
3
30
30
30
50
50
99
99
99
92
89
2
1
0.5
aReaction conditions: aryl bromide (1 mmol), phenyl boronic acid (1.2 mmol), K2CO3 (2 mmol), 3 M LiCl (1 ml) in i‐PrOH and water as solvent (1:1, 1 ml) at
room temperature.
bIsolated yield.
TABLE 2 Screening the efficiency of solvent and base for coupling of aryl bromides and phenyl boronic acida
Entry
Solvent
Base
Time (h)
Yieldb (%)
1
H2O
K2CO3
2
70
2
ETOH/H2O (1:1)
K2CO3
K2CO3
Na2CO3
Et3N
4
60
96
40
30
40
30
70
65
40
3
i‐PrOH/H2O (1:1)
0.5
3
4
i‐PrOH/H2O (1:1)
5
–
5
6
i‐PrOH/H2O (1:1)
Et3N
3
7
EtOH
–
Et3N
3
8
K2CO3
NaHCO3
Cs2CO3
5
9
i‐PrOH
H2O
4
10
4
aReaction conditions: aryl bromide (1 mmol), phenyl boronic acid (1.2 mmol), PdCl2 (2 mol%), 3 M LiCl (1 ml) at room temperature.
bIsolated yield.
etc.[21a,21b,21c,21d] At present, we are not clear whether any
one of these parameters or combination of all work for
LiCl‐promoted Suzuki–Miyaura cross‐coupling reactions.
Literature reports also suggest that the complexation of
PdCl2 and LiCl results in the in situ formation of a
water‐soluble complex, Li2PdCl4, which is believed to
catalyse the Suzuki–Miyaura cross‐coupling reaction. It
was noteworthy that a longer reaction time for the com-
pletion of the reaction with a comparatively decreased
yield of the product was observed when the reaction was
performed in the absence of LiCl.
view.[21e] The level of recyclability of the prepared
nanocatalytic system was investigated by consecutive
Suzuki–Miyaura cross‐coupling of 4‐bromoanisole and
phenyl boronic acid. After the first reaction cycle, diethyl
ether was added to the reaction mixture followed by cen-
trifugation and the clear organic layer was separated,
which was then evaporated to get the desired product.
The recovered catalyst system consisting of Pd nanoparti-
cles, LiCl (aq.)/i‐PrOH was immediately used in the 2nd
reaction cycle by adding fresh reactants. Almost identical
results were obtained till the 5th cycle of consecutive reac-
tions, which confirmed its efficiency as a reusable catalyst
without significant loss of its catalytic activity at least up
to five times (Table 4, entries 1–5).
Reusability of a heterogeneous catalyst serves as an
important factor in determining the efficiency of a catalyst
both from an economic and a green chemistry point of

4 of 7
PHUKAN ET AL.
TABLE 3 Pd (0) catalyzed Suzuki–Miyaura reactions using aryl
3.1 | Characterization of the isolated
catalyst
bromides and arylboronic acidsa
Generally, salts of PdCl2, Na2PdCl2, etc. are used as pre-
cursors for the preparation of palladium nanoparticles.
In our procedure, when PdCl2 is added to a mixture of
3 M LiCl, phenyl boronic acid and base (K2CO3), appear-
ance of black colour of the solution results within just a
few seconds (Figure 1). The reaction mixture was stirred
for 10 min to ensure complete reduction of Pd (II) salts.
The resulting mixture was completely black in colour,
which was then centrifuged and washed several times
with organic solvents, such as ether, hexane, ethyl
acetate, acetone to obtain pure palladium nanoparticles.
The washed catalyst was then oven‐dried at 80 °C for
6 h in order to get the dried powdered form of the
catalyst.
Morphology, sizes and characterization of the parti-
cles were determined by various techniques viz. trans-
mission electron microscopy (TEM), scanning electron
microscopy (SEM), dynamic light scattering (DLS), X‐
ray diffraction (XRD), TGA and Zeta potential. Figure 2
depicts some of the images of the newly synthesized Pd
nanoparticles from TEM. It has been seen that the aver-
age size of the particles ranges from 2 to 20 nm, and are
mostly spherical in shape (Figure 2a–c). Some of the par-
ticles are found in agglomerated form (Figure 2c). From
high‐resolution (HR)‐TEM, lattice spacing between two
adjacent planes of the synthesized nanoparticle was
found to be 0.22 nm (Figure 2b), which is characteristic
for Pd metallic nanoparticles. SEM was performed to
determine the morphology of the nanoparticles deposited
on the surface, and most of the particles were found to
be cuboidal in shape (Figure 1; Supporting Information).
Some of the SEM images are shown in Figure 1a–d
(Supporting Information). TEM results represent the
nanosize of Pd nanoparticles, where in SEM images
these nanoparticles have agglomerated in the sample
and adopted well‐engineered shapes, such as cuboidal
along with hexagonal, after drying. Composition of Pd
nanoparticles in the newly prepared powdered sample
was determined by dispersive X‐ray spectroscopy
(EDX), which showed a strong signal in the palladium
region indicating the formation of Pd nanoparticles
(Figure 1; Supporting Information). The XRD pattern of
the newly synthesized Pd nanoparticles is shown in
Figure 2 (Supporting Information). Prominent Bragg's
diffracted peaks were observed at 2ɵ values of 40.63°,
46.32° and 66.43°, which are assigned to be from (111),
(200), (220) crystal planes of Pd nanoparticles.
Yieldb
(%)
Entry R1‐Br
R2‐B(OH)2
Time
1
1.5 h
97
2
3
30 min 98
4 h
70
4
5
2 h
2 h
95
96
6
7
8
9
45 min 97
45 min 98
4 h
4 h
80
75
10
4 h
96
11
12
2 h
1 h
94
97
5 h
70
13
14
30 min 97
aReaction conditions: aryl bromide (1 mmol), arylboronic acid (1.2 mmol),
PdCl2 (2 mol%), K2CO3 (2 mmol), 3 M LiCl (1 ml); i‐PrOH:H2O (1:1, 1 ml)
at room temperature.
Dynamic light scattering and Zeta potential measure-
ments were performed to evaluate the hydrodynamic radii
of nanoparticles and surface charge of Pd nanoparticles.
bIsolated yield.

PHUKAN ET AL.
5 of 7
TABLE 4 Recyclability of the catalytic systema
Entry
Run
Time (min)
Yieldb (%)
1
1st
30
98
2
3
4
5
2nd
3rd
4th
5th
30
30
50
90
96
96
84
78
aReaction conditions: aryl bromide (1 mmol), phenyl boronic acid (1.2 mmol), PdCl2 (1 mol%), 3 M LiCl (1 ml), K2CO3 (2 mmol), i‐PrOH:H2O (1:1, 1 ml) at room
temperature.
bIsolated yield.
FIGURE 1 Preparation of palladium nanocatalyst. (a) mixture of boronic acid, K2CO3, 3 M LiCl. (b) addition of PdCl2 to (a). (c) instant
change of colour after addition of PdCl2 to (a). (d) reaction mixture before centrifugation. (e) reaction mixture after centrifugation. (f) dried
powder form of prepared catalyst
Zetasizer Nano ZS light scattering apparatus (Malvern
Instruments, UK) with a He − Ne laser (633 nm, 4 mW)
at an angle of 90° where filtered solution through
0.22‐μm membrane filter was directly transferred into the
cuvette. The intensity weighted size distribution (Figure 2
d) showed that nanoparticles have average hydrodynamic
radii from 20 to 60 nm, with maximum intensity at 38
nm. The larger size was observed due to agglomeration of
Pd nanoparticles in solution. This size measurement vali-
dates the size measured from TEM. The Zeta potential
value for Pd nanoparticles was also measured to check
their colloidal stability, and the value of zeta potential
was found to be near to 0.75 mV, which is far from the
required value for stability. This indicates nil surface
charge of the nanoparticles, and as a consequence they
tend to agglomerate in the dispersion medium.

6 of 7
PHUKAN ET AL.
FIGURE 2 TEM images of palladium nanoparticles (a–c) and intensity‐weighted DLS of Pd nanoparticles (d) (yellow circle showing
nanoparticle and arrow bars showing d‐spacing)
REFERENCES
4 | CONCLUSION
[1] M. Forough, K. Farhadi, Turkish J. Eng. Env. Sci. 2010, 34, 281.
In summary, we have developed an efficient and very
quick method for the synthesis of biaryls using rapid in
situ‐generated palladium nanoparticles. The newly gener-
ated in situ catalyst has been analyzed by several character-
ization techniques, such as TEM, SEM–EDX, XRD and
TGA. Moreover, it plays an effective role in the Suzuki–
Miyaura cross‐coupling reactions of activated aryl halides
and aryl boronic acids, providing a significant yield of the
desired coupled products at room temperature.
C. B. Hwang, Y. S. Fu, S. J. Yu, J. Catal. 2000, 195, 336. S.
Forster, M. Antonietti, Adv. Mater. 1998, 10, 195. S. M.
Marinakos, D. A. Shultz, D. L. Fldheim, Adv. Mater. 1999, 11,
134. G. Schmid, Chem. Rev. 1992, 92, 1709.
[2] (a) Y. Sun, Y. Xia, Science 2002, 298, 2176. (b) J. Chen, J. M.
McLellan, A. Siekkinen, Y. Xiong, Z.‐Y. Li, Y. Xia, J. Am. Chem.
Soc. 2006, 128, 14 776. (c) J. W. Stone, P. N. Sisco, E. C.
Goldsmith, S. C. Baxter, C. J. Murphy, Nano Lett. 2007, 7, 116.
(d) B. Wiley, Y. Sun, Y. Xia, Acc. Chem. Res. 2007, 40, 1067.
(e) B. Kumari, D. P. Singh, Ecol. Eng. 2016, 97, 98.
[3] (a) H. Li, L. Han, J. Cooper‐White, I. I. Kim, Green Chem. 2012,
14, 586. (b) H. Sharma, M. Bhardwaj, M. Kour, S. Paul, J. Mol.
Catal. 2017, 435, 58. (c) A. Pourjavadi, A. Motamedi, Z.
Marvdashti, S. H. Hossein, Catal. Commun. 2017, 97, 27. (d)
X. Cui, Y. Zheng, M. Tian, Z. Dong, J. Mol. Catal. 2017, 433,
202. (e) K. Anand, C. Tiloke, A. Phulukdaree, B. Ranjan, A.
Chuturgoon, S. Singh, R. M. Gengan, J. Photochem. Photobiol.
2016, 165, 87.
ACKNOWLEDGEMENTS
The authors acknowledge the Department of Science and
Technology for financial assistance under DST‐FIST
program and UGC, New Delhi for Special Assistance
Programme (UGC‐SAP) to the Department of Chemistry,
Dibrugarh University. The authors thank the Analytical
Division of CSIR‐CSMCRI for analytical facilities.
[4] (a) J. S. Albero, G. Rupprechter, H. Freund, J. Catal. 2005, 52,
235. (b) M. Q. Zhao, R. M. Crooks, Angew. Chem. Int. Ed.
1999, 38, 364.
ORCID
[5] X. M. Chen, G. H. Wu, J. M. Chen, X. Chen, Z. X. Xie, X. R.
Diganta Sarma http://orcid.org/0000-0001-5174-418X
Wang, J. Am. Chem. Soc. 2011, 133, 3693.

PHUKAN ET AL.
7 of 7
[6] H. J. Lee, S. E. Habas, G. A. Somorjai, P. D. Yang, J. Am. Chem.
Soc. 2008, 130, 5406.
Liu, O. Palchik, Y. Koltypin, A. Gedanken, Langmuir 2000,
16, 6396. (d) L. P. Jiang, J. R. Zhang, J. Wang, J. J. Zhu, Chinese
J. Inorg. Chem. 2002, 18, 1161.
[7] N. Tian, Z. Y. Zhou, N. F. Yu, L. Y. Wang, S. G. Sun, J. Am.
Chem. Soc. 2010, 132, 7580.
[17] M. Iida, S. Ohkawa, N. Asaoka, H. Yoshikawa, Chem. Lett. 2002,
10, 1050.
[8] N. Dimitratos, F. Porta, L. Prati, Appl. Catal. 2005, 291, 210.
[18] A. A. Athawale, S. V. Bhagwat, P. P. Katre, A. J. Chandwadkar,
[9] Z. Hou, N. Theyssen, A. Brinkmann, W. Leitner, Angew. Chem.
Int. Ed. 2005, 44, 1346.
P. Karandikar, Mater. Lett. 2003, 57, 3889.
[19] C. Y. Wang, Y. Zhou, Z. Y. Chen, Q. Y. Lu, X. Mo, J. Nanopart.
Res. 1999, 1, 479.
[10] (a) E. H. Rahim, F. S. Kamounah, J. Frederiksen, J. B.
Christensen, Nano Lett. 2001, 1, 499. (b) V. Calo, A. Nacci, A.
Monopoli, P. Cotugno, Angew. Chem.,Int. Ed. 2009, 48, 6101.
(c) Y. Li, X. M. Hong, D. M. Collard, M. A. El‐Sayed, Org. Lett.
2000, 2, 2385. (d) K. Sawai, R. T. Nakahodo, H. Fujihara,
Angew. Chem. Int. Ed. 2008, 47, 6917. (e) J. Ge, C. Yaun, C.
Zhang, J. Jiang, M. Liu, Tetrahedron Lett. 2017, 58, 1142. (f)
M. Gholinejad, M. Bahrami, C. Najera, J. Mol. Catal. 2017,
433, 12. (g) J. Zhang, T. Li, X. Zhao, Y. Zhao, F. Li, X. Li,
J. Colloid Interface Sci. 2016, 463, 13. (h) A. Kumar, G. K. Rao,
S. Kumar, A. K. Singh, Organometallics 2014, 33, 2921.
[20] Y. Xiong, J. M. McLellan, J. Chen, Y. Yin, Z. Y. Li, Y. Xia, J. Am.
Chem. Soc. 2005, 127, 17 118.
[21] (a) D. Sarma, A. Kumar, Org. Lett. 2006, 8, 2199. (b) D. Sarma, S.
S. Pawar, S. S. Deshpande, A. Kumar, Tetrahedron Lett. 2006,
47, 3957. (c) D. Sarma, A. Kumar, Appl. Catal. A Gen. 2008,
335, 1. (d) A. Kumar, Chem. Rev. 2001, 101, 1. (e) P. R. Boruah,
A. A. Ali, B. Saikia, M. Chetia, D. Sarma, Chem. Commun. 2015,
51, 11 489.
[11] C. Vincenzo, N. Angelo, M. Antonio, D. Antonia, I. Patrizia,
SUPPORTING INFORMATION
Organometallics 2003, 22, 4193.
Additional Supporting Information may be found online
in the supporting information tab for this article.
[12] (a) Y. Li, E. Boone, M. A. El‐Sayed, Langmuir 2002, 18, 4921. (b)
C. Liu, Q. Ni, P. Hu, Z. Qui, Org. Biol. Chem. 2011, 9, 1054. (c) C.
Liu, X. Li, Z. Gao, X. Wang, Z. Jin, Tetrahedron 2015, 71, 3954.
[13] J. C. G. Martinez, R. Lezutekong, R. M. Crooks, J. Am. Chem.
Soc. 2005, 127, 5097.
How to cite this article: Phukan P, Boruah PR,
Gehlot PS, Kumar A, Sarma D. A simple, quick and
novel protocol for biaryl synthesis using LiCl‐
promoted in situ‐generated Pd nanoparticles. Appl
Organometal Chem. 2017;e4009. https://doi.org/
10.1002/aoc.4009
[14] V. Kogan, Z. Aizenshtat, R. Popovitz‐Biro, R. Neumann, Org.
Lett. 2002, 4, 3529.
[15] (a) A. Dhas, A. Gedanken, J. Mater. Chem. 1998, 8, 445. (b) K. S.
Suslick, M. Fen, T. Hyeon, J. Am. Chem. Soc. 1996, 118, 11 960.
[16] (a) X. Qui, J. Xu, J. Zhu, S. Xu, H. Chen, J. Mater. Res. 2003, 18,
1399. (b) Y. Mastai, R. Polsky, Y. Koltypin, A. Gedanken, G.
Hodes, J. Am. Chem. Soc. 1999, 121, 10 047. (c) J. J. Zhu, S. W.