Bimetallic Ni–Pd Synergism—Mixed Metal Catalysis of the Mizoroki-Heck Reaction and the Suzuki–Miyaura Coupling of Aryl Bromides

Article abstract of DOI:10.1007/s10562-020-03330-9

Abstract: A combination of Pd and Ni complexes activated aryl bromides for the thermal Mizoroki-Heck reaction and Suzuki coupling giving high yields in short reaction times. A thermal redox mechanism probably occurs whereby Ni complex transfers electron and reduces the Pd (II) to Pd (0) which then takes the reactants through the standard protocol of oxidative-addition, migratory insertion and reductive elimination, typical for the Mizoroki-Heck reaction and the Suzuki coupling. Graphic Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-020-03330-9

Catalysis Letters
https://doi.org/10.1007/s10562-020-03330-9
Bimetallic Ni–Pd Synergism—Mixed Metal Catalysis
of the Mizoroki‑Heck Reaction and the Suzuki–Miyaura Coupling
of Aryl Bromides
Abhijit A. Kashid1 · Dharmaraj J. Patil1 · Ramling D. Mali1 · Vijay P. Patil1 · T. V. Neethu1 · Heena K. Meroliya3 ·
Shobha A. Waghmode3 · Suresh Iyer1,2
Received: 26 May 2020 / Accepted: 21 July 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
A combination of Pd and Ni complexes activated aryl bromides for the thermal Mizoroki-Heck reaction and Suzuki cou-
pling giving high yields in short reaction times. A thermal redox mechanism probably occurs whereby Ni complex transfers
electron and reduces the Pd (II) to Pd (0) which then takes the reactants through the standard protocol of oxidative-addition,
migratory insertion and reductive elimination, typical for the Mizoroki-Heck reaction and the Suzuki coupling.
Graphic Abstract
Keywords Bimetallic catalysis · Mizoroki-Heck · Suzuki coupling · Nickel complexes · Pd(OAc)2
1 Introduction
Synergistic interaction of bimetallic catalysts cause
Electronic supplementary material The online version of this
increased activity & efciency compared to monometallic
article (https://doi.org/10.1007/s10562-020-03330-9) contains
catalysis [1]. State of the art, bimetallic nano alloy archi-
supplementary material, which is available to authorized users.
tectures demonstrate conservatism in the noble metal usage
* Suresh Iyer
s.iyer@ncl.res.in
and increased catalyst activity. Bimetallic nano clusters con-
jure a magical wizardry associated with catalyst activation
known for the efcient catalysis of several reactions [2–20].
No studies with mixed metal complexes is reported for the
Mizoroki-Heck reaction or Suzuki coupling. The activation
of aryl bromides and chlorides is essential atom economy
in several cross coupling reactions thus making them suit-
able for industrial applications [21]. The use of tert-Bu3P,
1
Organic Chemistry Division, National Chemical Laboratory,
Dr. Homi Bhabha Road, Pashan, Pune, Maharashtra 411008,
India
2
3
Academy of Scientifc and Innovative Research (AcSIR),
New Delhi 110025, India
Abasaheb Garware College, Karve Road, Pune,
Maharashtra 411004, India
Vol.:(0123456789)
1 3

A. A. Kashid et al.
phosphite ligands, additives like PPh4Cl, dimethyl glycine,
NHC ligands, special sterically bulky ligands and bases, pal-
ladacycles, ionic liquids are some of the solutions for aryl
bromide and chloride activation for the Mizoroki-Heck reac-
tion and Suzuki–Miyaura coupling [22–46].
added [Pd] (2.5 mol %) and Ni complex (5 mol %). After
degassing with argon, the resulting mixture was heated with
stirring at 150 °C for 1–12 h under argon. After completion
of reaction (monitored by TLC), the reaction mixture was
quenched by adding 10% HCl. The solution was extracted with
ethyl acetate (3×20 ml) the combined extract was washed with
saturated brine and dried over anhydrous Na2SO4. The organic
layer was concentrated under vacuum and the crude product
purifed by column chromatography on silica gel (100–200
mesh, Petroleum ether or Petroleum Ether: 2–5% Ethyl ace-
tate) to give pure product.
Bimetallic nano alloys of noble metal Pd merged with
non noble metal Fe, Co, Ni ramps up catalysis for various
reactions like hydrogenation. Here, noble metal usage is con-
served leading to an inexpensive alternative and merger with
non noble metal conjuring a magical boosting of activity and
efciency [12–25]. Bozell and Vogt exploited this synergism
of NiBr2 with Pd(OAc)2 as bimetallic catalyst for the Mizo-
roki-Heck reaction of aryl chlorides but requiring addition of
excess NaI [47]. Ni complexes, Cu salts and heterogeneous
Ni, Cu, Co and Mn are good catalysts for the Mizoroki-Heck
reaction of aryl iodides and bromides [48–53]. Ligand free
Pd(OAc)2 has been reported to catalyze the Mizoroki-Heck
reaction of aryl bromides requiring long reaction times of
19–44 h [54]. In related studies in our laboratory, bimetallic
catalyst systems of Ni–Pd-supported on ABPBI (polybenzi-
midazole) polymer and Ni–Pd QD (quantum dots) were used
to catalyze the Mizoroki-Heck reaction and Suzuki–Miyaura
coupling of aryl halides [55, 56]. Bimetallic Ni–Pd alloys
have demonstrated enhanced activity in Sonogashira cou-
pling and Suzuki coupling [12, 15, 57, 58]. This enhanced
activity can be explained as being due to a redox couple with
electron transfer from Ni to Pd which generates high electron
density on Pd and thus enhances reduction of Pd (II) to Pd
(0). This increases the rate of oxidative addition step in the
catalytic cycle [15]. Based on this we proposed the con-
servative synergism of Ni complexes with Pd(OAc)2 for the
activation of aryl bromides for the Mizoroki-Heck reaction
and the Suzuki–Miyaura coupling. Ligands on Nickel and
Pd would thus enhance the reactivity enabling the electron
transfer from Ni to Pd.
Benzene, 1-methoxy-4- [(1E)-2-phenylethenyl]- (6 h,
0.151 g, 72%, 0.72 mmol, White solid, MP-136 °C) CAS
Registry Number 1694–19-5 2 1H NMR (CHLOROFORM-
d, 200 MHz): δ (ppm) 7.31–7.69 (m, 7H), 7.17 (d, J=7.5 Hz,
2H), 7.05 (d, J=8.7 Hz, 2H), 3.97 (s, 3H); 13C NMR (CHLO-
ROFORM-d, 50 MHz): δ (ppm) 159.4, 137.7, 130.2, 129.5,
128.7, 128.4, 128.4, 128.3, 128.2, 127.8, 127.7, 127.3, 126.7,
126.3, 114.2, 113.6, 113.0, 77.7, 77.1, 76.5, 55.4; IR (cm−1)
2920, 2854, 2344, 2288, 1605, 1384, 1313, 1120, 1038, 865,
773, 714, 661; HRMS-ESI: [M+ +H]+ calcd for C15H15O,
211.112 found: 211.111.
2.2 General Procedure for the Bimetallic (Ni–Pd)
Catalysis of Aryl Bromides for the Suzuki
Coupling
To a solution of aryl halide (0.5 mmol), aryl boronic acid
(0.073 g, 0.6 mmol), TBABr (0.161 g, 0.5 mmol) and K3PO4
(0.127 g, 0.6 mmol) in dioxane and water (1:1, 10 ml) was
added Pd(OAc)2 (0.005 g, 0.03 mmol, 2.5 mol%) and [Ni]
complex (5 mol %). The resulting mixture was heated with
stirring at 130 °C for 2–6 h under argon. After completion
of reaction (monitored by TLC), the reaction mixture was
quenched with 10% HCl. The solution was extracted with
ethyl acetate (3×20 ml) the combined extract was washed with
saturated brine and dried over anhydrous Na2SO4. The organic
layer was concentrated under vacuum and the crude product
purifed by column chromatography on silica gel (100–200
mesh, Petroleum Ether) to give pure product.
Recently, the use of Ni–Pd binary nanoclusters for the
Suzuki–Miyaura coupling of hindered, ortho-heterocycle
tethered, aryl bromides and carbonates has been reported
[59, 60]. In this letter we describe the bimetallic catalysis
of the thermal Mizoroki-Heck reaction and Suzuki coupling
with a mixture of Ni and Pd metal salts and complexes,
showing enhanced activity.
1,1′- Biphenyl, 4-methyl- (4.5 h, 0.076 g, 0.45 mmol, 90%
yield, white solid, MP–49 °C) CAS Registry Number 644-08-6
1H NMR (CHLOROFORM-d, 200 MHz): δ=7.17−7.63 (m,
9 H), 2.39 ppm (s, 3 H); IR (cm−1)–2926, 2372, 2112, 1592,
1413, 1122, 1043, 859, 814, 752; HRMS-ESI: [M++H]+ calcd
for C13H13 [M+ +H]+ 169.102 found: 169.101.
2 Experimental Procedures
2.1 General Procedure for Bimetallic Catalysis
of Mizoroki‑Heck Reaction of Various Aryl
Bromides
3 Results and Discussion
To a solution of aryl bromide (1 mmol), alkene (1-2 mmol),
TBABr (Tetrabutylammonium bromide) (1 mmol) and base
(1.2 mmol) in NMP (1-methyl-2-pyrrolidinone) (5 ml) was
Preliminary screening with various Ni complexes and
Pd(OAc)2 showed the bimetallic complexes to be active for
the Mizoroki-Heck reaction of 4-bromo anisole and ethyl
1 3

Bimetallic Ni–Pd Synergism—Mixed Metal Catalysis of the Mizoroki-Heck Reaction and the Suzuki–…
Scheme 1 Ni–Pd catalyzed
Mizoroki-Heck reaction of
4-bromoanisole with ethyl
acrylate
Table 1 Ni–Pd catalyzed Mizoroki-Heck reaction of 4-bromoanisole
Pd(OAc)2, 2.5 mol %
[Ni], 5 mol %
Br
W
with ethyl acrylate
+
W
S. No. Cat-A
Cat-B
Time (h) Yield (%) (E)
K2CO3, TBABr
NMP, 150 oC
R
R
Yield : 52 - 87 % E
1
2
3
4
5
6
7
8
Pd(OAc)2
Pd(OAc)2-PPh3
Pd(OAc)2
HB-PdCycle
Pd(OAc)2
Pd(OAc)2
None
None
Ni[P(OPh)3]4
Nibpy3Cl2
Nien3Cl2
Ni[DMG]2
48
18
1
1.3
1.3
1.5
2.30
63
53
62
77
51
37
67
78
58
78
76
92
63
45
52
80
78
54
R : H, 4-CH3O, 4-CH3, 4-Cl, 4-OH, 1-Nap, 4-C6H5 W : COOC2H5, C6H5
Scheme 2 Ni–Pd catalyzed Mizoroki-Heck reaction of various aryl
bromides
PdCl2(CH3CN)2 Ni-[8-HQ]2
From these results one could assume that P(OPh)3, PPh3
are very good ligands on Ni in conjunction with Pd(OAc)2
while bpy is equally good but taking longer reaction times
of 26 h. NiSalen and Ni SALPHEN both gave lower yields
of 52–54% requiring longer reaction times also of 24–36 h.
This phenomena could be due to higher electron density
attributed to the phosphine ligands compared to the nitro-
gen ligand; while use of palladacycles gives better yields in
shorter times. All these results were from unoptimized reac-
tions. The reaction catalyzed by Pd(OAc)2 only, with no Ni
co-catalyst, proceeded slowly in 48 h and moderate yield of
63% [54]. Addition of PPh3 as ligand reduced the reaction
time to 18 h with yield of 53%.
PdCl2(PPh3)2
Oxime PdCycle
Pd(OAc)2
Ni[P(OPh3)]4 3.3
NiCl2(PPh3)2 3.30
NiCl2(PPh3)2
9
10
11
12
13
14
15
16
17
18
6
Bedford-PdCycle Nien3Cl2
10.1
13.5
14.5
22
24
25
Pd(OAc)2
Pd(OAc)2
Pd[P(OPh)3]4
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
[Ni(acac)2]3
NiBr2
Nibpy3Cl2
NiSalen
Ni-[8-HQ]2
Nibpy3Cl2
NiSalphen
26
36
Reaction conditions: 4-Bromoanisole (1 mmol), Ethylacrylate
(1–2 mmol), K2CO3 (1.2 mmol), TBABr (1 mmol), Pd Cat (2.5 mol
%), Ni (Co-Cat) (5 mol %), NMP (5 ml), Argon
The reaction of diferent aryl bromide with styrene and
ethyl acrylate was then experimented with combinations
of Pd and Ni complexes (Scheme 2; Table 2). A 1:2 ratio
of Pd to Ni complexes was efective catalyst. A 1: 10 ratio
was also found efective for the Mizoroki-Heck reaction of
4-bromo anisole and ethyl acrylate. Apart from Pd(OAc)2,
we also tried some Pd complexes and palladacycles as cata-
lysts along with diferent Ni complexes as co-catalyst. The
Herrmann Pd cycle gave very high yield of 77% in 1.3 h in
conjunction with Nibpy3Cl2 as co-catalyst.
acrylate (Scheme 1). Moderate to high yields were obtained
(Table 1) and the results are shown in increasing time of
reaction. A standard protocol for the Mizoroki-Heck reac-
tions was used for these bimetallic catalyzed reactions in
NMP as solvent. The reaction catalyzed by Ni[P(OPh)3]4 &
Pd(OAc)2 was the fastest being complete in 1 h with high
yield of 62% E-isomer. Ni(bpy)3Cl2 was completed in 1.3 h
but moderate yield of 51%. But the use of Herrmann-Beller
Pdcycle with Nibpy3Cl2 gave higher yield of 77% in 1.3 h.
Reaction times of 1.5–6 h was achieved with Ni[DMG]2 (Ni-
Dimethylglyoxime), Ni[8-HQ] (Ni-8-Hydroxyquinoline),
Ni[P(OPh)3]4, and NiCl2(PPh3)2 with yields in the range of
51–78%. The Pd catalysts were Pd(OAc)2, PdCl2(CH3CN)2,
PdCl2(PPh3)2, and Oxime PdCycle. The reaction with Oxime
Pdcycle gave a lower yield of 58% compared to the catalysis
with Pd(OAc)2 which gave 78% yield but in 6 h, longer time.
The reaction with [Ni(acac)2]3 gave the highest yield of 92%
in 13.5 h. NiBr2, Nibpy3Cl2 (bpy-bipyridyl), Ni Salen, Ni-
[8-HQ]2, Ni Salphen, in conjunction with Pd(OAc)2 took
longer times of 14.5–36 h with good yields of 45–80%.
The Bedford PdCycle also gave high yield of 76% with
co-catalyst Nien3Cl2 though in 10.1 h. Reaction catalyzed
by the acetophenone oxime Pd cycle and NiCl2(PPh3)2 also
was fast, being complete in 3.30 h but with 58% yield. These
reactions were not optimized. We then chose Ni[P(OPh)3]4
as the co-catalyst for exploring the reactions of various sub-
stituted aryl bromides.
We have earlier reported the catalysis of the Mizoroki-
Heck reaction by Ni[P(OPh)3]4 and CuI separately [8]. The
mixed metal catalysed reactions were complete in 2–6 h
at 130–150 °C with yields ranging from 52 to 87%. The
Table 2 is organized with comparison of the results of reac-
tions of various aryl bromides and ethyl acrylate (EA) and
1 3

A. A. Kashid et al.
Table 2 Ni–Pd catalyzed
Mizoroki-Heck reaction of
various aryl bromides
S. No.
Aryl bromide
Alkene
Catalyst A
Catalyst B
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
C6H5Br
C6H5Br
EA
Styrene
EA
Styrene
EA
Styrene
EA
EA
Styrene
EA
Styrene
EA
EA
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
NiCl2(PPh3)2
Ni[P(OPh)3]4
Ni[P(OPh)3]4
Ni[P(OPh)3]4
Ni[P(OPh)3]4
Ni[P(OPh)3]4
NiCl2(PPh3)2
Ni[P(OPh)3]4
Ni[P(OPh)3]4
NiCl2(PPh3)2
Ni[P(OPh)3]4
Ni[P(OPh)3]4
NiCl2(PPh3)2
Ni[P(OPh)3]4
Ni[P(OPh)3]4
Ni[P(OPh)3]4
Ni[P(OPh)3]4
2.15
8
5
6
4.15
4
2.15
2.20
3.5
6
85a
67a
70a
72a
67a
52a
60a
60a
63b
65a
75c
65c
69a
57a
69a
87b
80b
4-CH3OC6H4Br
4-CH3O·C6H4Br
4-CH3C6H4Br
4-CH3C6H4Br
4-Cl·C6H4Br
4-Cl·C6H4Br
4-Cl·C6H4Br
4-HO·C6H4Br
4-HO·C6H4Br
4-HO·C6H4Br
1-Nap·Br
9
10
11
12
13
14
15
16
17
7
5.3
4.5
2.1
6
3
2
1-Nap·Br
Styrene
Styrene
EA
4-C6H5C6H4·Br
4-C6H5C6H4·Br
2-CHO·C6H4·Br
Styrene
Reaction conditions: ArBr 1 mmol, Alkene 1–1.5 Eq, Base: 1.2 mmol, TBABr–1 mmol, NMP–5 mL,
Pd(OAc)2–2.5 mol %, [Ni]–5 mol %, 130–150 °C
EA ethyl acrylate
Base: aK2CO3, bCy2NMe, cCs2CO3
styrene. A few examples were tried with Pd(OAc)2 (cat)
and NiCl2(PPh3)2 co-catalyst, for comparison, which gave
high yield of 85% with bromo benzene and ethyl acrylate
in 2.15 h. While K2CO3 was the base of choice, 4-bromo
phenol gave better results with Cs2CO3 as base. Cy2NMe
(N,N-Dicyclohexylmethylamine) was also an efective base
for some of the reactions. Highest yield of 87% was obtained
from 4-bromobiphenyl and ethyl acrylate in 3 h, catalysed
by Pd(OAc)2 and Ni{P(OPh)3]4. CuI as a co-catalyst did not
activate the reaction of 4-bromo anisole with ethyl acrylate
or styrene.
shortest time of 2 h in the reaction of 4-chlorobromoben-
zene with phenyl boronic acid catalyzed by Pd(OAc)2 and
NiCl2(PPh3)2. All the Ni complexes tried, Ni[P(OPh)3]4,
NiCl2(PPh3)2, Ni[DMG]2, NiSalen, Nien3Cl2, Nibpy3Cl2,
Ni-[8-HQ]2 were synergistically fast with Pd(OAc)2, giv-
ing very high yields of 82–93% and in short reaction times
of 2–6 h. A variety of aryl bromides reacted with difer-
ent aryl boronic acids and all gave high yields showing
generality.
The formation of Pd–Ni bimetallic nano clusters has been
reported to be the active catalyst form in similar reactions
demonstrated by Reetz and Chakraborti though their system
is slightly diferent from the reaction conditions used by us
[58, 59]. We believe that a homogeneous catalysis mecha-
nism is in operation here though some complexes might be
proceeding via partly nano particle catalysis. The catalysts
used are homogeneous and visual observations do not show
any colloidal particles in the reaction mixture thus confrm-
ing a homogeneous catalysis.
The reactions were also energized by visible light giv-
ing very high yields and which results will be reported
elsewhere. The Suzuki coupling of aryl bromides was
also investigated with the Pd–Ni bimetallic catalysts
(Scheme 3; Table 3). The reactions were carried out in a
part aqueous solvent system of dioxane: water (1:1) with-
out any surfactants, with the bimetallic Pd(OAc)2 and [Ni]
catalysts. The highest yield of 93% was obtained in the
Scheme 3 Ni–Pd catalysis of
the Suzuki coupling of Aryl
bromides
1 3

Bimetallic Ni–Pd Synergism—Mixed Metal Catalysis of the Mizoroki-Heck Reaction and the Suzuki–…
Table 3 Pd–Ni Bimetallic catalysis of the Suzuki coupling of aryl bromides
S. No.
Aryl bromides
Aryl boronic acid
[Ni] Co-catalyst
Product
Time (h)
Yield (%)
1
2
3
4
5
6
7
4-CH3·C6H4Br
4-Cl·C6H4Br
4-CH3·C6H4Br
4-CH3O·C6H4·Br
1-Nap·Br
4-C6H5·C6H4Br
4-CH3O·C6H4·Br
C6H5B(OH)2
C6H5B(OH)2
4-ClC6H4B(OH)2
C6H5B(OH)2
1-Nap·B(OH)2
2-NapB(OH)2
1-Nap·B(OH)2
Ni[P(OPh)3]4
NiCl2(PPh3)2
Ni[DMG]2
NiSalen
Nien3Cl2
Nibpy3Cl2
Ni-[8-HQ]2
4-CH3·C6H4·C6H5
4-Cl·C6H4·C6H5
4-CH3·C6H4·C6H4.-Cl
4-CH3O·C6H4·C6H5
1,1′-Binaphthalene
2-Nap-C6H4-4-C6H5
4-CH3O·C6H4.Nap-1
4.5
2
3
90
93
82
88
92
89
90
6
2.5
4.2
2.5
Reaction conditions: ArBr (0.5 mmol), Aryl boronic acid (0.6 mmol), K
%) Dioxane:Water (1:1. 10 ml), Argon, 130 °C
3PO4 (0.6 mmol), TBABr (0.5 mmol), Pd Cat (2.5 mol %), Ni Cat (5 mol
The mechanism of the catalysis could be explained
thus; electron transfer occurs from Ni complex or salts
to Pd (II) increasing the electron density on Pd reduc-
ing it to Pd(0), thus making it more nucleophilic which
activates the oxidative addition to aryl bromides. This is
then followed by the standard protocol catalytic cycle for
the Mizoroki-Heck reaction and Suzuki coupling. Further
studies are underway to confrm the nature of this bimetal-
lic catalysis and will be the subject of a full paper.
References
1. Narayanan R (2010) Molecules 15(4):2124
2. Polshettiwar V, Asefa T (2013) Nanocatalysis: synthesis and appli-
cations. Wiley, Hoboken
3. Pye DR, Mankad NP (2017) Chem Sci 8(3):1705
4. Astruc D (2007) Transition metal nanoparticles in catalysis: from
historical background to the state of the art. Nanoparticles and
Catalysis. Wiley, Weinheim
5. Zaleska-Medynska A, Marchelek M, Diak M, Grabowska E
(2016) Adv Coll & Inter Sci 229:80
6. Peng L, Ringe E, Van Duyne RP, Marks LD (2015) Phy Chem
Chem Phy 17(42):27940
7. Notar Francesco I, Fontaine-Vive F, Antoniotti S (2014) Chem-
CatChem 6(10):2784
4 Conclusions
8. Tao FF (2012) Chem Soc Rev 41(24):7977
9. Sankar M, Dimitratos N, Miedziak PJ, Wells PP, Kiely CJ, Hutch-
ings GJ (2012) Chem Soc Rev 41(24):8099
We have thus demonstrated a convenient bimetallic Ni–Pd
catalyst protocol for the Mizoroki-Heck reaction and the
Suzuki coupling of aryl bromides. The reactions proceed
in convenient short times giving high yields. The Mizo-
roki-Heck reaction retains the E-selectivity. The mixture
of Ni[P(OPh)3]4 and Pd(OAc)2 is an efective combination
for the desired fast reactions of Mizoroki-Heck and Suzuki
coupling while NiCl2(PPh3)2 and Pd(OAc)2 is comparable
in activity and provides high yields. Further studies are
underway to elucidate the mechanism. Most probably a
redox mechanism is proceeding with a transfer of electrons
from Ni to Pd under thermal conditions. This facilitates
the formation of Pd (0) which then undergoes the well-
established oxidative addition—reductive elimination pro-
tocol as understood for the Mizoroki-Heck reaction and the
Suzuki–Miyaura coupling.
10. Sharma G, Kumar A, Sharma S, Naushad M, Prakash Dwivedi R,
Alothman ZA, Mola GT (2017) J King Saud Univ Sci 31:257–269
11. Sinfelt JH (1983) Bimetallic catalysts: discoveries, concepts and
applications. Wiley, Hoboken
12. Son SU, Jang Y, Park J, Na HB, Park HM, Yun HJ, Lee J, Hyeon
T (2004) J Amer Chem Soc 126(16):5026
13. Feng L, Chong H, Li P, Xiang J, Fu F, Yang S, Hui Y, Sheng H,
Zhu M (2015) J Phy Chem C 119(21):11511
14. Wu Y, Wang D, Zhao P, Niu Z, Peng Q, Li Y (2011) Inorg Chem
50(6):2046
15. Rai RK, Tyagi D, Gupta K, Singh SK (2016) Cat Sci & Tech
6(10):3341
16. Smith SE, Siamaki AR, Gupton BF, Carpenter EE (2016) RSC
Adv 6(94):91541
17. Ohtaka A, Sansano JM, Nájera C, Miguel-García I, Berenguer-
Murcia Á, Cazorla-Amorós D (2015) ChemCatChem 7(12):1841
18. Kyriakou G, Boucher MB, Jewell AD, Lewis EA, Lawton TJ,
Baber AE, Tierney HL, Flytzani-Stephanopoulos M, Sykes ECH
(2012) Science 335(6073):1209
19. Lorion MM, Maindan K, Kapdi AR, Ackermann L (2017) Chem
Soc Rev 46(23):7399
Acknowledgements Financial support from the CSIR Network Project,
ORIGIN—under XII Five year plan CSC 0108 and PA-II post to VPP
is gratefully acknowledged.
20. Fu J, Huo X, Li B, Zhang W (2017) Org & Bio Chem 15(46):9747
21. Whitcombe NJ, Hii KKM, Gibson SE (2001) Tetrahedron
57(35):7449
22. Reetz MT, Westermann E (2000) Angew Chem Int Ed 39(1):165
23. Reetz MT, Breinbauer R, Wanninger K (1996) Tet Lett
37(26):4499
Compliance with Ethical Standards
Conflict of interest There are no conficts to declare.
1 3

A. A. Kashid et al.
24. Littke AF, Fu GC (2001) J Amer Chem Soc 123(29):6989
25. Beller M, Zapf A (1998) Synlett 1998(7):792
26. Reetz MT, Lohmer G, Schwickardi R (1998) Angew Chem Int Ed
37(4):481
45. Kitamura Y, Sako S, Udzu T, Tustsui A, Maegawa T, Monguchi
Y, Sajiki YH (2007) Chem Commun 47:5069
46. Kostas ID, Tenchiu A-C, Arbez-Gindre C, Psycharis V, Rapto-
poulou CP (2014) Cat Commun 51:15
27. Reetz MT, Westermann E, Lohmer R, Lohmer G (1998) Tet Lett
39(46):8449
47. Bozell JJ, Vogt CE (1988) J Amer Chem Soc 110:2655
48. Sustmann R, Hopp P, Holl P (1989) Tet Lett 30(6):689
49. Kelkar AA, Hanoka T, Kubota Y, Sugi Y (1994) Cat Lett
29(1–2):69
28. Reetz MT, de Vries JG (2004) Chem Commun 14:1559
29. Ben-David Y, Portnoy M, Gozin M, Milstein D (1992) Organomet
11(6):1995
50. Iyer S, Ramesh C, Ramani A (1997) Tet Lett 38(49):8533
51. Iyer S, Ramesh C, Sarkar A, Wadgaonkar PP (1997) Tet Lett
38(46):8113
30. Portnoy M, Ben-David Y, Milstein D (1993) Organomet
12(12):4734
31. Portnoy M, Ben-David Y, Rousso I, Milstein D (1994) Organomet
13(9):3465
52. Iyer S, Thakur VV (2000) J Mol Cat A Chem 157:275
53. Handa S, Slack ED, Lipshutz BH (2015) Angew Chem Int Ed
54(41):11994
32. Lauer MG, Thompson MK, Shaughnessy KH (2014) J Org Chem
79(22):10837
54. Yao Q, Kinney EP, Yang Z (2003) J Org Chem 68(19):7528
55. Patil VP, Kashid AA, Solanki BS, Kharul UK, Iyer S (2020)
(Paper submitted to Heliyon)
33. Herrmann WA, Brossmer C, Öfele K, Reisinger C-P, Priermeier T,
Beller M, Fischer H (1995) Angew Chem Int Ed Eng 34(17):1844
34. Herrmann WA, Brossmer C, Reisinger C-P, Riermeier TH, Öfele
K, Beller M (1997) Chem A Eur J 3(8):1357
56. Raut PK, Meroliya HK, Dumbre SR, Sudhakaran S, Waghmode
SA, Iyer S (2020) (Paper to be communicated)
35. Herrmann WA, Elison M, Fischer J, Köcher C, Artus GRJ (1995)
Angew Chem Int Ed Eng 34(21):2371
57. Phukan P, Boruah PR, Gehlot PS, Kumar A, Bordoloi A, Sarma
D (2017) Chem Select 2(35):11795
36. Herrmann WA, Broßmer C, Öfele K, Beller M, Fischer H (1995)
J Mol Cat A: Chem 103(3):133
58. Metin Ö, Ho SF, Alp C, Can H, Mankin MN, Gültekin MS, Chi
M, Sun S (2012) Nano Res 6(1):10
37. Iyer S, Ramesh C (2000) Tetrahedron Lett 41:8981
38. Iyer S, Jayanthi A (2001) Tetrahedron Lett 42:7877
39. Iyer S, Jayanthi A (2003) Synlett 2003(8):1125
40. Alonso DA, Najera C (2010) Chem Soc Rev 39:2891
41. Santos CIM, Barata JFB, Faustino MAF, Lodeiro C, Neves
MGPMS (2013) RSC Adv 3:19219
59. Seth K, Purohit P, Chakraborti AK (2014) Org Lett 16(9):2334
60. Purohit P, Seth K, Kumar A, Chakraborti AK (2017) ACS Catal
7(4):2452
Publisher’s Note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional afliations.
42. Iyer S, Kulkarni GM, Ramesh C (2004) Tetrahedron 60:2163
43. Kostas ID, Tenchiu A-C, Arbez- Gindre C, Psycharis V, Rapto-
poulou CP (2014) Cat Commun 51:15
44. Wolfe JP, Singer RA, Yang BH, Buchwald SL (1999) J Amer
Chem Soc 121(41):9550
1 3