Ferrocene catalysed C–H arylation of arenes and reaction mechanism study using cyclic voltammetry

Article abstract of DOI:10.1016/j.tetlet.2016.08.020

Ferrocene catalysed C–H arylation of benzene using aryldiazonium salt is studied. Yield of biphenyl in this reaction was found to be better than some of the known methods. Aryldiazonium salts with electron withdrawing groups produced excellent yields (upto 85%) in C–H arylation. Applicability of this reaction was studied on several arenes and heteroarene such as benzene, naphthalene, anthracene, pyrene and pyridine. Catalytic role of ferrocene in aryl radical formation was studied by cyclic voltammetry of phenyldiazonium tetrafluoroborate. In presence of ferrocene more radical formation was observed. This reaction model works at ambient temperature and features the use of inexpensive catalyst for the synthesis of biaryl derivatives.

Full text of DOI:10.1016/j.tetlet.2016.08.020

Accepted Manuscript
Ferrocene catalysed C-H arylation of arenes and reaction mechanism study using
cyclic voltammetry
Swati Dixit, Qamar Tabrez Siddiqui, Mohammad Muneer, Neeraj Agarwal
PII:
S0040-4039(16)31007-3
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.08.020
TETL 47991
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
12 June 2016
5 August 2016
6 August 2016
Please cite this article as: Dixit, S., Siddiqui, Q.T., Muneer, M., Agarwal, N., Ferrocene catalysed C-H arylation of
arenes and reaction mechanism study using cyclic voltammetry, Tetrahedron Letters (2016), doi: http://dx.doi.org/
1
0.1016/j.tetlet.2016.08.020
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Graphical Abstract
Ferrocene catalysed C-H arylation of arenes
and reaction mechanism study using cyclic
voltammetry
Leave this area blank for abstract info.
S. Dixit, Q. T. Siddiqui, M. Muneer and N. Agarwal*
CV of C6H5N2BF4 with increasing [Fc]
0.00000
N BF
2
4
Ferrocene
Arene
substrate
-0.00008
[Fc]
+
R
Acetone, RT
-
-
0.00016
0.00024
1
4 examples
R
Yield upto 85 %
Cyclic voltammetry provides insight on the radical
formation in the initial steps of reaction
-0.6
-0.3
0.0
Potential/V

1
Tetrahedron Letters
Ferrocene catalysed C-H arylation of arenes and
reaction mechanism study using cyclic voltammetry
a
a,b
b
a
Swati Dixit , Qamar Tabrez Siddiqui , Mohammad Muneer and Neeraj Agarwal 
a
UM-DAE, Centre for Excellence in Basic Sciences, University of Mumbai, Kalina campus, Santacruz (E), Mumbai 400098, India
b
Department of Chemistry, Aligarh Muslim University, Aligarh, 202002, India
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Ferrocene catalysed C-H arylation of benzene using aryldiazonium salt is studied. Yield of
biphenyl in this reaction was found to be better than some of the known methods.
Aryldiazonium salts with electron withdrawing groups produced excellent yields (upto 85%) in
C-H arylation. Applicability of this reaction was studied on several arenes and heteroarene such
as benzene, naphthalene, anthracene, pyrene and pyridine. Catalytic role of ferrocene in aryl
radical formation was studied by cyclic voltammetry of phenyldiazonium tetrafluoroborate. In
presence of ferrocene more radical formation was observed. This reaction model works at
ambient temperature and features the use of inexpensive catalyst for the synthesis of biaryl
derivatives.
Available online
Keywords:
C-H arylation
Ferrocene
Catalysis
2
009 Elsevier Ltd. All rights reserved.
Biaryl motifs have several applications in areas such as
synthesis of catalysts, synthesis of chiral ligand, optoelectronic
materials, enzyme inhibitors and medicines. Several cyano
toxicity of some transition metals. Also, these methods are not
economically viable.
1
In recent times, addition of aryl radicals to arenes followed by
elimination of hydrogen radical have been reported. Several
methods have been developed for the aryl radical formation
reactions. Dediazoniation of aromatic diazonium salts, aryl
halides with radical generator have been used as aryl radical
source albeit with limited use. Transition metal-free approaches
have emerged as an alternate choice for aryl-aryl couplings
biphenyls with long aliphatic tails are in demand for commercial
grade liquid crystal display technologies and in organic light
2
emitting devices. A class of dye family derived from benzidine
3
is popularly used in commercial dyes and polymers. Biaryls with
different substituents are commonly used as building blocks for
4
synthesis of polycyclic aromatic compounds. Synthesis of
biphenyls or biaryls require the carbon-carbon bond formation
(Scheme 1).
(C-H arylation) and can be achieved by several methods. Some
of the classical methods are Ullmann reaction, Scholl reaction,
Gomberg-Bachmann reaction, Grignard reaction etc. The yield
1,10-Phenanthroline
diamine or diol, DMSO
5
R
R
+
R
in these reactions is poor, also they have very limited
applications due to sensitive reaction conditions. Several groups
have reported the synthesis of biaryls using transition metal
catalysed coupling reactions (e.g. Suzuki, Negishi, Stille,
t
KO Bu
Eosin Y or C60
+
R
t
KO Bu, h,
6
Kumada, Hiyama etc). These coupling reactions require aryl
NO2
halides/triflates and coupling partners such as boronic acids,
sodium sulfinates, silanes, and organotin compounds. Later,
copper and silver catalysed coupling between aryl boronic acids
t
KO Bu, DMSO
NH
+
NO2
N
H
7,8
and heteroaryls were developed. Unarguably transition metal
catalyzed approaches are very popular to synthesize biphenyl
Scheme 1: Transition metal-free approaches for C-H arylation
9
derivatives. However, these methods are not suitable for the
t
In 2009, Itami et al reported KO Bu promoted coupling of
synthesis of biaryls for biological applications due to inherent
10
11
12
heteroarenes with aryl iodides. Shi et al, Hayashi et al and
1
3
other groups reported the similar synthesis of biaryls using
—
——

Corresponding author. Tel.: +91-22-26530227; fax: +91-22-26524982; e-mail: na@cbs.ac.in

2
Tetrahedron
unactivated arenes and aryl halides in the presence of base. In
inductive effect of groups present on aryldiazonium salts. It was
found that excellent yields were obtained when electron-
withdrawing groups were substituted on phenyl (2-4 of Table 1).
Electron-donating groups produced lesser yield of biaryls (5, 6 of
Table 1). Groups ortho to amino also produced relatively lesser
yield (7, 8 of Table 1) and can be attributed to steric effect.
some of these cases N-heteroaryl ligands, or catalytic amount of
diamine and diols were also used as ligand. Ligand binds with
metal ion to form an intermediate and promotes the single
electron transfer. Rossi et al and Li et al recently showed light
driven (photocatalytic) direct arylation of benzene with KO Bu in
DMSO. Konig et al developed metal and base free Eosin Y
catalysed photocatalytic approach for CH arylation. Chan et al
used porphyrin, phthalocyanine and fullerene as organocatalyst
for C-H arylation.
of KO Bu-mediated C-C coupling in phenols and benzamides
14
t
15
1
6
N2BF4
Ferrocene (10 mol%)
Arene
+
16b-e
R
Very recently Sangit et al explored the use
substrate
Acetone, RT
t
R
17a,b
using aryl halide coupling partners.
the KO Bu-mediated intermolecular oxidative C-C coupling of
nitroarenes with indoles.
Same group has reported
t
R
CF3
NO2
17b
R
N
The arylation of benzene and other accessible bromoarenes
require the use of light, heat and catalyst to get the aryl-aryl bond
formation. Yuan et al recently showed the direct arylation of
R= H, 1; CN, 2; NO2, 3; R= Cl, 7; NO2, 8
Cl, 4; SMe, 5; OH, 6;
9
10
t
18
benzene with aryl halide and 1,10-phenanthroline and KO Bu.
N
These reaction conditions ensure the aryl radical formation as the
intermediate which was proved by electron papamagnetic
resonance (EPR) methods. Ferrocene catalysed efficient and cost
effective reaction for C-H arylation of BODIPY using
11
12
13
14
19
Scheme 2: Synthesis of ferrocene catalysed biaryl derivatives.
phenyldiazonium tetrafluoroborate was developed. Ferrocene in
this reaction is believed to catalyze the aryl radical formation
which prompted us to use aryldiazonium salt for the direct
arylation of benzene. Here, in this report, we studied the general
applicability of ferrocene catalysed arylation on several arenes
and heteroarene such as benzene, naphthalene, anthracene,
pyrene and pyridine. Catalytic role of ferrocene in the formation
of aryl radical was studied by cyclic voltammetry of
aryldiazonium tetrafluoroborate in the presence of ferrocene.
This reaction model works at ambient temperature and features
the use of inexpensive catalyst for the synthesis of biaryl
derivatives.
This method of arylation is applicable to various arene
substrates such as naphthalene, anthracene and pyrene and also
on heteroarene such as pyridine. In general, yields obtained are
good to excellent. In some examples, yield obtained is better than
the previously reported methods. All these compounds were
characterized by several spectroscopic methods. Experimental
details and related spectra are provided in supporting
information.
Table 1: Arylation of arenes with aryldiazonium tetrafluoroborate
a
Aryl diazonium salt
Arene
Yield Product
%)
(
Aryldiazonium tetrafluoroborates were prepared using aryl
amines and tetrafluoroboric acid (HBF
dissolved in aqueous solution of HBF at 0 C and solution of
NaNO at 0 C was added to it slowly. Aryldiazonium
tetrafluoroborate precipitated out during the reaction. On
completion of reaction solid was filtered and washed with cold
water. Various aryldiazonium tetrafluoroborate salts bearing
electron-withdrawing or electron-donating groups were
4
). Aryl amine was
84
85
1
2
3
4
5
6
7
4
N BF
2
4
2
NC
N BF
2
4
synthesized.
These
freshly
prepared
aryldiazonium
8
7
5
1
5
7
O N
2
N BF
2
tetrafluoroborates were used to synthesize the biaryl derivatives.
To optimize the reaction conditions, phenyldiazonium
tetrafluoroborate and benzene were used as reactants and acetone
as solvent. Ferrocene dissolved in acetone was used as catalyst.
Reaction of phenyldiazonium tetrafluoroborate (1 eq), benzene (3
eq) and ferrocene (10 mol%) in acetone proceeded smoothly at
room temperature in 2 h. The desired 1,1’-biphenyl was obtained
in 84% yield. The yield obtained in this reaction is found to be
higher than some of the literature methods. A few other organic
solvents such as dichloromethane, DMSO and DMF were also
tested as reaction medium to understand the suitability and
adaptability of this reaction. Poor yields (less than 30%) were
obtained in DMSO and acetonitrile while no reaction was
observed in dichloromethane probably due to insolubility of
4
Cl
N BF
2
4
MeS
HO
N BF
2 4
44
N BF
2
4
Cl
6
7
N BF
2
4
3
aryldiazonium salt. Solvents such as CHCl and THF produced a
complex mixture of products. In the absence of ferrocene
reaction proceeds very slowly and produced biphenyl in poor
yield (~ 10%).
NO2
N BF
78
8
2
4
Several derivatives of aryl and heteroaryl diazonium
tetrafluoroborate were used to synthesize the biaryl derivatives
(Table 1). The yield of the products depends, fairly, on the

3
a
concentration of ferrocene suggests the formation of more
Aryl diazonium salt
Arene
Yield Product
%)
phenyl radicals (Figure 1). These results suggest that ferrocene is
catalyzing the formation of phenyl radicals. Aryl radical
generation through single electron transfer should be prominent
in case of electron deficient aryl diazonium salts and hence
results in better yields (2-4).
(
8
2
9
O N
2
N BF
2 4
F3C
6
8
5
7
1
6
10
11
12
N
N BF
2 4
O N
N BF
4
N
2
2
N BF
2
4
4
4
4
2
13
14
N BF
2
2
1
N BF
2
Figure 1. Cyclic voltammograms of phenyldiazonium tetrafluoroborate
(6.5 mM) with increasing concentration of ferrocene recorded in acetonitrile.
a
Isolated yields
Reaction mechanism for ferrocene catalysed C-H arylation is
Dehaen et al. have proposed a radical reaction mechanism for
ferrocene catalysed C-H arylation on BODIPY. We recently
studied similar reaction using EPR experiments and found
evidences of radical formation in initial steps which was further
expected to be radical mediated as proposed in Figure 2. In the
initial step, single electron transfer (SET) from ferrocene to
aryldiazonium salt produces aryl radical which further takes part
in the reaction. We investigated the formation of aryl radicals by
cyclic voltammetry. The formed aryl radical reacts with arene
followed by electron transfer to ferrocenium ion and
subsequently hydrogen abstraction to complete the reaction. Aryl
radical generation from diazonium salts is believed to be a fast
reaction and is unlikely to be the rate determining step. To get an
insight on the rate determining step competition reaction between
benzene and benzene-d is carried out. The K /K value was
19b
supported by DFT calculations. Aryl diazonium salts usually
20
accept single electron to form aryl radicals. Aryl radicals
formed may undergo several possible reactions (i) homo-
coupling of radical, (ii) abstraction of protons from solvents in
2
1
turn production of solvent radicals, and so on. To get the insight
on the reduction and, eventually, the radical formation of
phenyldiazonium
tetrafluoroborate
we
studied
the
6
H
D
1
electrochemical behavior of phenyldiazonium tetrafluoroborate
using cyclic voltammetry. The figure 2 shows the voltammogram
of phenyldiazonium tertrafluoroborate in acetonitrile (6.5 mM)
determined by the H NMR (See supporting information) and is
found to be ~ 1 which implies that C-H bond cleavage is not rate
determining step. On the basis of these results the rate-
determining step may be the bond formation between aryl radical
and arene.
on glassy carbon as working electrode at a scan rate of 1 V/sec. A
red
p
broad irreversible wave ( E ) was observed at -0.25 V/Ag,AgCl.
Irreversibility of reduction peak indicates the dissociation of
diazonium salt on electron transfer. Tiny bubbles were visible in
solution during the potential scan, possibly evolution of nitrogen
gas. Further, on second scan this reduction peak shifted towards
more negative potential and later in successive scans disappeared.
In higher concentration of phenyldiazonium tetrafluoroborate
similar shift in the reduction potential was observed however no
reduction peak was observed when very high concentration (13
mM) or slow scan rate (50 mV/sec) was used. Pinson et al
explained this on the basis of reaction of phenyl radicals with
active electrode area which causes the changes in electrode
2
1b
property.
To study the effect of ferrocene on reduction of aryldiazonium
salt we carried out the cyclic voltammetry of a mixture of salt
and increasing concentration of ferrocene (0-0.15 M). Glassy
carbon electrode was washed and cleaned thoroughly after every
measurement to nullify the effect of electrode blocking.
Reduction current was found to be increasing with increase of
ferrocene concentration while having the constant concentration
of phenyldiazonium tetrafluoroborate. Also peak potential shifted
towards more negative values. Increase in current as well as
shifting of reduction peak potentials with increasing
Figure 2: Proposed reaction mechanism for ferrocene catalysed C-H
arylation.

4
Tetrahedron
Conclusions
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formation was observed in the presence of ferrocene.
Applicability of this reaction is tested on several arenes and
heteroarene such as benzene, naphthalene, anthracene, pyrene
and pyridine. This reaction model works at ambient temperature
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7
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5
Highlights
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



Synthesis of biaryl derivatives using
ferrocene as catalyst is described
Arenes and aryldiazonium tetrafluoroborate
were used as reactants
C-H arylation was successfully employed
on several arenes
Reaction pathway was studied using cyclic
voltammetry
Ferrocene catalysed C-H arylation is elegant
and simple to perform