Nickel-glycerol: An efficient, recyclable catalysis system for Suzuki cross coupling reactions using aryl diazonium salts

Article abstract of DOI:10.1039/c5nj01833a

Nickel catalysed Suzuki reactions of phenyl boronic acids with aryl diazonium salts in glycerol as a reaction medium are reported. Various aryl diazonium salts were efficiently reacted with aryl boronic acids under optimized conditions to give the respective diaryl compounds in good to excellent yields. The base free conditions and use of glycerol as a solvent, which can be recycled successfully for up to five consecutive cycles, make the present protocol environmentally benign in nature.

Full text of DOI:10.1039/c5nj01833a

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DOI: 10.1039/C5NJ01833A
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Nickel-glycerol: An efficient, recyclable catalysis system for Suzuki cross
coupling reaction using aryl diazonium salt
Jeevan Manohar Bhojane, a Sachin Ashok Sarode, a and Jayashree Milind Nagarkar a*
Received 00th January
20xx,
Accepted 00th January
20xx
Nickel catalysed Suzuki reaction of phenyl boronic acid with aryl diazonium salt in glycerol as a reaction
medium has been reported. Various aryl diazonium salts were efficiently reacts with aryl boronic acids under
optimized conditions to give respective diaryl compounds in good to excellent yield. The base free
conditions, use of glycerol as a solvent which can be recycled successfully upto five consecutive cycles have
made the present protocol environmentally benign in nature.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Keywords: Aryl diazonium salt, Aryl boronic acid, NiCl2-glyme,Glycerol, Suzuki reaction
Introduction
Transition metal catalysed cross coupling reactions play an without bases.38-42 The reagent used for this cross coupling
important role in organic synthesis. Particularly, Suzuki reaction is organoboronic reagent which is stable in air and
reaction is a powerful tool for the construction of C-C bond easily available.43 It possesses low toxicity, and high moisture
using palladium catalyst.1-7 Its major applications are in the resistance. Due to growing awareness about environmental
pharmaceuticals, fine chemicals and agro industries.8 The issues, researchers have diverted their attention to develop
cross coupling reactions are commonly catalysed by palladium. environment friendly route as an alternative to conventional
However the first row transition elements such as Ni, Co, Fe processes. Recently various researchers have reported
and Cu are also used as alternative to palladium in cross different cross coupling reactions in aqueous medium as they
coupling reactions.9-14 Use of Nickel as catalyst in many cross are environmentally benign and inexpensive.44-48 However,
coupling reactions namely Suzuki Miyaura reaction,15-17 aqueous medium imposes some limitations such as low
Sonogashira reaction,18-20 Negishi reaction21-23 is well known. solubility of starting material and lower heating temperature
Its use as a catalyst serves two purposes viz. it is inexpensive as compared to other organic solvents. Hence new greener
than palladium and produces low residual metal content in the routes for cross coupling reactions are developed which are
reaction mass.24 The Suzuki reaction catalysed by using nickel environmentally benign. Cross coupling reactions are well
as a catalyst follow similar mechanism as that of palladium.25-26
Aryl halide is the most common reagent used for such cross
coupling reactions. However, the high cost and low reactivity
of these substrates limits their application and the use of C-O
or C-N electrophiles such as carbamates, sulfamates and
tosylates have been gained much attention in various organic
transformations.27-28 Recently the most interesting research is
carried out with popular electrophilic partner such as aryl
diazonium salts. Diazonium salts have several advantages over
aryl halides. They can be easily prepared from inexpensive
aniline, which is more reactive than aryl halides.29-32 Diazonium
salts were used for various cross coupling reactions such as C-
N, C-S, and C-O bond formation reactions.33-37 The Suzuki
reaction is studied using diazonium salt at lower temperature
aDepartment of Chemistry, Institute of Chemical Technology, Matunga, Mumbai
400 019, India.*E-mail:jm.nagarkar@ictmumbai.edu.in
,
Scheme1 General scheme for Suzuki cross coupling reaction
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reported using greener and recyclable solvents like ionic liquid, increased from 69% to 86% after addition of DMSO (Table 2,
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PEG and Glycerol.49-53 Glycerol is economical and entry 1). Some the reaction DMSO usDeOdI: a10s.10o3x9id/Ca5nNtJ.60118W33Ae
environmentally safer solvent due to its physico-chemical carried out the reaction in the absence of glycerol more or less
properties such as high boiling point, high polarity, same yield of cross coupling product as well as homo coupling
biodegradability, low flammability and high solubility for product of diazonium salt were obtained (Table 2, entry 5).
organic and inorganic compounds.54-60 All above facts and The reaction carried out nitrogen atmosphere and afforded
observations prompted us to explore catalytic activity of nickel 84% yield of desired product was obtained (Table 2, entry 6).
for Suzuki reaction by using glycerol as solvent and diazonium
salt as starting material.
Table2 Effect of co solvent
Result and Discussion
Entry
Catalyst
Co solvent
DMSO
Yieldb
86
We initially chose phenyl boronic acid and diazonium salt of
aniline as starting material for optimization of Suzuki reaction
using nickel chloride as precatalyst and glycerol as solvent. The
reaction mixture stirred at 80°C for 12h afforded 42 % yield of
the desired product. Various nickel precatalysts were screened
for the optimization of reaction conditions. First we carried out
reaction in the absence of precatalyst and obtained trace
amount of desired product (Table 1, entry 1).It was found that,
reaction carried out using NiCl2.glyme gave maximum yield as
compared to other nickel precatalysts (Table 1, entries 2-8).
This catalyst is easily available, and also air and moisture
stable. The yield of desired product was found to increase with
catalyst loading from 5 to 10 mol%. Further rise in catalyst
loading from 10 to 15 mol% gave marginal increase in the yield
(Table 1, entries 6, 9and 10).
1
2
3
4
5
6
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
DMF
64
Methanol
MeCN
32
43
44c
84d
DMSO
DMSO
aReaction Conditions: Aryl diazonium salt (1.2 mmol), aryl boronic acid
(1 mmol), NiCl2.glyme 10 mol%, glycerol (2mL), co solvent (0.5mL),
Temperature: 80 °C for 12h, bIsolated yield
d N2 atmosphere.
.
C absence of glycerol,
The effect of temperature was studied from room
temperature to 80 °C (Table 3, entries 1- 4). The reaction not
initiated at room temperature however, increasing the
reaction temperature from room temperature to 40 °C gives
45% yield of desired product. Further rise in temperature from
40 to 80 °C, increases yield from 45% to 90% in 12 h (Table 3,
entries 2-4).To optimize reaction time, we performed reactions
at different time intervals (Table 3, entries 5,6). It was
observed that reaction after 8 h under optimized conditions
gave only 59% yield (table 3, entry 5) whereas increasing the
reaction time to 16 h did not show much improvement in the
yield (table 3, entry 6).
Table1 Screening and optimization of catalyst
Entry
1
Catalyst
-
Yieldb
Trace
2
3
4
5
NiCl2
NiSO4
NiCl2(PPh3)2
Ni(OAc)2
42
31
18
46
Table3 Effect of temperature and time for nickel catalysed
Suzuki reaction
6
7
NiCl2. Glyme
Ni(acac)2
61
25
Entry
Catalyst
Temp.
RT
Yieldb
15
8
Ni(COD)2
54
1
2
3
4
5
6
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
NiCl2. glyme
9
NiCl2. Glyme
52c
69d
40
45
10
NiCl2. Glyme
60
63
aReaction Conditions: Aryl diazonium salt (1.2 mmol), aryl boronic acid
(1 mmol), Catalyst 10mol%, glycerol (2 mL), Temperature 80 °C for 12
h, bIsolated yield%, ccatalyst 5mol%, dcatalyst 15mol%.
80
90
59c
90d
80
80
a Reaction Conditions: Aryl diazonium salt (1.2 mmol), aryl boronic acid
Different solvents such as DMSO, DMF, Methanol and MeCN
were screened to select suitable co-solvent (Table 2, entries 1-
4). Homocoupling of diazonium salt was observed in methanol
as co solvent, whereas presence of MeCN gave acetanilide as
major product. Amongst studied solvents DMSO was found to
the be most favourable solvent as yield of desired product was
b
(1 mmol), NiCl2.glyme (10 mol%), glycerol (2 ), DMSO (0.5mL);
Isolated yield, reaction time 12 h; c reaction time: 8 h; d reaction time:
16 h.
Reactions of various substituted aryl diazonium salts with
phenyl boronic acid compounds were carried out under
2 | J. Name., 2012, 00, 1-3
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optimized reaction conditions. It was observed that, aryl substituent at para position with phenyl diazonium salt
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diazonium salt with electron donating substituents at para containing electron donating substituent DaOt I:o1r0th.1o03p9/oCs5itNiJo0n18a3n3dA
position gave comparatively higher yields(Table 4,entries3- electron withdrawing substituent at para position (Table 4,
4)than that present at ortho or meta position (Table 4,entries entries 13,14). Reaction of 4-methoxy phenyl boronic acid with
2,5).The electron withdrawing substituents such as NO2, CN diazonium salt of 2-methyl aniline gives moderate yield (Table
and CF3 gave good yield of desired products (Table 4, entries 6- 4, entry 13), on the other hand it gives comparatively higher
9). Diazonium salt substituted with halogens such as –F, –Cl yield with diazonium salt of 4-nitro aniline (table 4, entry 14).
and –Br showed chemo-selective coupling reaction (Table 4, Reaction of 4-fluro phenyl boronic acid with diazonium salt of
entries 10-12).We also examined synthesis of unsymmetrical 4-methoxy aniline was found to give higher yield of respective
diaryls using phenyl boronic acid containing electron donating unsymmetrical diaryl product (Table 4, entry 15).
Table 4 Substrate studya
Entry
1
Aryl boronic acid
Aryl diazonium salt
Product
Yieldb
90
2
3
4
1a
1a
1a
73
84
87
5
6
75
76
1a
1a
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DOI: 10.1039/C5NJ01833A
7
74
1a
8
9
71
77
79
1a
1a
1a
10
11
12
82
80
1a
1a
13
70
14
15
1b
76
77
a Reaction Conditions: Aryl diazonium salt (1.2 mmol), Aryl boronic acid (1 mmol), NiCl2.glyme (10 mol %), DMSO(0.5mL), glycerol (2 mL), temperature: 80°C
for 12 h, b Isolated yield.
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Table 5 Recyclability study
Conclusion:
Scheme2 Plausible mechanism for Suzuki cross coupling
reaction
In conclusion, we have developed an efficient, economical, base
free protocol for Suzuki cross coupling reaction. The protocol is cost
effective as diazonium salts is a cheaper arylating source than aryl
halides and also NiCl2 glyme is a cheaper catalyst than palladium
complexes. DMSO used as a co solvent increases the yield of the
desired product. The protocol is applicable to a variety of diazonium
salts and boronic acid giving good to excellent yields of desired
product. Recyclability of the homogeneous catalyst upto five cycles
and used of glycerol as the green solvent are merits of this protocol.
On the basis of previous reports we propose a plausible mechanism
for the Nickel catalysed Suzuki reaction (Scheme 2). Initially there is
in situ generation of Ni (0) species due to glycerol62. The reaction
may proceed either via single electron transfer (SET) or oxidative
addition mechanism.63 Path A, followed SET mechanism where Ni
(0) is converted into Ni (I) intermediate A by the oxidative addition
of aryldiazonium salt which immediately gets converted into
intermediate C. In path B oxidative addition of aryl diazonium salt
converts Ni(0) to Ni(II) which immediately gets transformed into
Intermediate C. Aryl boronic acid gets complex with intermediate C
which facilitates the subsequent transfer of the phenyl group to
nickel complex (transmetalation) intermediate D. In the final step
there is formation of C-C bond by reductive elimination which
generates Ni (0) catalyst. We are still working on this mechanism.
Experimental section
General: All chemicals were purchased from Sigma Aldrich, S.D Fine
Chemical, Avra, Spectrochem Ltd, Loba Chemmie and commercial
suppliers and used without further purifications. 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 X 0.25). The product mass
conformed by GC–MS-QP 2010 instrument (Rtx-17, 30 m_25 mm
ID, film thickness 0.25 μm, column flow: 2 mLmin–1, 80 to 240 °C at
10 °C/ min rise). The products were purified by column
chromatography using (60-120 mesh) silica gel with pet ether as
eluent. The pure product 1H NMR Spectroscopic data of compounds
was recorded on a Varian Mercury plus- 300 spectrometer using
DMSO and CDCl3 as a solvent and TMS as internal standard.
NiCl2.glyme has been synthesized by known literature method. Aryl
diazonium tetraboroflourate are synthesis by known method.
The catalyst and solvent recyclability study was performed using
diazonium salt of aniline with phenyl boronic acid. After completion
of reaction, the product was extracted in ethyl acetate and the
glycerol layer containing Nickel catalyst was used for next run. The
results obtained were summarized in Table 5. It was found that,
the catalyst and solvent can be efficiently recycled over five runs
without any significant loss in the product yield.
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General procedure for Suzuki coupling with aryl diazonium salt
3-nitro-1, 1’-biphenyl (3g) 27: Pale yellow solid; yield: 0.146 g (74%);
mp 57-59°C. H NMR: (300 MHZ, d- DMSO, TMS):  8.42(s, 1H, Ar-
1
To an oven-dried 25 mL schlenk tube equipped with a magnetic
stirring bar was charged with arene diazonium salt (1.2mmol),
phenyl boronic acid (1 mmol), NiCl2.glyme (10 mol %), followed by
anhydrous DMSO (0.5mL), glycerol (2 mL). Reaction mixture was
stirred at 80°C for 12 h. The reaction was monitored by GC and TLC.
After completion of the reaction, the reaction mixture was diluted
with ethyl acetate. The resulting ethyl acetate layer was washed
with water and 20% brine solutions. The organic layer was dried
over anhydrous sodium sulphate. The solvent was removed under
vacuum to get the crude product, which was purified by column
chromatography on silica gel eluting with the pet ether (100%) to
afford the pure product. The purity and identity of known products
are conformed by 1H NMR and GC-MS Spectroscopic techniques.
The glycerol layer contained catalyst was used for further reactions.
H),8.25 (d, 1H, Ar-H),7.79(t,2H, Ar- H), 7.54(dd,4H,Ar-H),
7.42(s,1H,Ar-H). GC-MS m/z (% relative intensity): 199(M+, 100),
169(43), 152(96), 127(9), 115(15), 102(6),87(3), 76(15)
2-(trifluoromethyl)-1, 1’-biphenyl (3h)7: colourless liquid; yield:
0.156 g (71%); GC-MS m/z (% relative intensity): 222(M+, 100),
201(13), 183(3), 172(3), 154(24), 152(27), 125(3), 111(6.36), 85(4)
[1, 1’-biphenyl]- 4- carbonitrile (3i) 36: White solid; yield: 0.136 g
(77%); mp 84-86°C. GC-MS m/z (% relative intensity): 179(M+, 100),
151 (13), 126(5), 113(2), 100(3),89(18), 73(10).
4-chloro -1, 1’-biphenyl (3j) 37: White solid; yield: 0.147 g (79%); mp
70-72°C. GC-MS m/z (% relative intensity): 188(M+, 100), 153(33),
152(58), 76(27).
Spectral data for the representative compounds
4-bromo -1, 1’-biphenyl (3k) 35: Off white solid; yield: 0.190 g (82%);
mp 89-90°C. 1H NMR: (300 MHZ, d- DMSO, TMS):  7.64(m, 2H, Ar-
H), 7.51(d, 2H, Ar -H), 7.55(m, 4H,Ar-H), 7.41(d,1H,Ar-H). GC-MS
m/z (% relative intensity): 232(M+, 77), 152 (100), 126(9), 116(5),
102(4), 87(3), 76(35).
Biphenyl (3a) 36: White solid; yield: 0.137 g (90%); mp 68-70°C. GC-
MS m/z (% relative intensity): 154(M+, 30), 105 (100), 77(60),
51(17)
2-methyl-1, 1’-biphenyl (3b) 35: Colourless liquid; yield: 0.121 g
(73%). GC-MS m/z (% relative intensity): 168(M+, 100), 167 (73),
152(27), 128(6), 115(14),102(4), 91(8), 82(10)
4-fluoro -1, 1’-biphenyl (3l) 12: White solid; yield: 0.137 g (80%); mp
71-73°C. 1H NMR: (300 MHZ, d- DMSO, TMS):  7.91(m, 4H,Ar-
H),7.75(d,2H,Ar-H), 7.49(m,3H,Ar-H).GC-MS m/z (% relative
intensity): 172(M+, 100), 146 (3), 133(3), 120(2), 85(9), 83(15).
4-methyl-1, 1’-biphenyl (3c) 35: Off white solid; yield: 0.142 g (84%);
mp 46-47°C. GC-MS m/z (% relative intensity): 168(M+, 100), 153
(43), 12(7), 115(13), 102(3), 91(6),89(8), 83(15).
4’- methoxy-2- methyl-1, 1’- biphenyl (3m) 12: Pale yellow solid;
yield: 0.137 g (70%); mp 120-122°C. GC-MS m/z (% relative
intensity): 198(M+, 100), 183 (16), 167(34), 153(11), 128(4), 115(6),
99(3), 89(3), 77(6).
4-methoxy-1, 1’-biphenyl (3d) 35: White solid; yield: 0.161 g (87%);
mp 87-89°C.1H NMR : (300 MHZ,d- DMSO, TMS):  7.61( d, 2H,Ar-
H), 7.59( d, 2H,Ar-H),7.45(d, 1H, Ar-H),7.32(d,2H,Ar-H), 7.02(d,
2H,Ar-H), 3.81(s,3H,CH3),,GC-MS m/z (% relative intensity): 184(M+,
100), 169(56.39), 141(57.10),139(14),115(43), 92(5), 76(8)
4- methoxy-4’- nitro-1, 1’- biphenyl (3n) 36: Pale yellow solid: 0.174
g (76%); mp 108-110°C. 1H NMR: (300 MHZ, d- DMSO, TMS):
8.28(d, 2H,Ar-H),7.91(d, 2H,Ar-H), 7.79(d, 2H,Ar-H), 7.10(d,2H,Ar-
H), 3.82(s,3H, CH3), GC-MS m/z (% relative intensity): 229(M+,
100), 214 (2), 199(2), 183(7), 168(45), 156(3), 140(26), 139(64),
113(4), 102(6), 89(5), 75(3).
3-methyl-1, 1’-biphenyl (3e) 27: Colourless liquid; yield: 0.125 g
(75%).GC-MS m/z (% relative intensity): 168(M+, 100), 167(62), 152
(25), 128(4), 115(8), 102(2), 91(6), 89(5), 83(10).
4-nitro-1, 1’-biphenyl (3f) 36: Yellowish solid; yield: 0.150 g (76%);
mp 110-112°C.1H NMR: (300 MHZ, d- DMSO, TMS):  8.32(d,2H,Ar-
H), 7.98(dd, 2H,Ar-H), 7.81(d, 2H,Ar-H), 7.58(d, 2H,Ar-H),7.45(m,
1H,Ar-H) GC-MS m/z (% relative intensity): 199(M+, 97), 152 (100),
127(9), 115(9), 102(5), 87(4), 76(20).
4- fluoro- 4’- methoxy-1, 1’- biphenyl (3o) 10: White solid; yield:
0.155 g (77%); mp 85-86°C. 1H NMR: (300 MHZ, d- DMSO, TMS):
7.63(d, 2H,Ar-H),7.58(m,2H, Ar-H), 7.26(d,2H, Ar-H), 7.02(d, 2H,Ar-
H), 3.79(s,3H –OCH3 ). GC-MS m/z (% relative intensity): 202(M+,
100), 187 (68), 170( 6), 159(64), 144(2) 133(47), 120(3), 101(7),
83(5)
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New Journal of Chemistry
Nickel-glycerol: An efficient, recyclable catalysis system for Suzuki cross coupling reaction using aryl diazonium salt
Jeevan Manohar Bhojane, Sachin Ashok Sarode, and Jayashree Milind Nagarkar *
Palladium free, chemo selective, environmental benign protocol for C-C bond formation reaction