BiCl3-catalyzed carbon-carbon cross-coupling of organoboronic acids with aryl iodides

Article abstract of DOI:10.1002/aoc.3020

A procedure for BiCl₃-catalyzed carbon-carbon cross-coupling reaction of organoboronic acids with aryl iodides is described. This protocol has a wide substrate scope and uses an inexpensive and non-toxic catalyst. Copyright

Full text of DOI:10.1002/aoc.3020

Full Paper
Received: 3 April 2013
Revised: 6 May 2013
Accepted: 16 May 2013
Published online in Wiley Online Library: 23 July 2013
(wileyonlinelibrary.com) DOI 10.1002/aoc.3020
BiCl -catalyzed carbon-carbon cross-coupling
3
of organoboronic acids with aryl iodides
†
Payal Malik, Desna Joseph and Debashis Chakraborty*
A procedure for BiCl -catalyzed carbon-carbon cross-coupling reaction of organoboronic acids with aryl iodides is described. This
3
protocol has a wide substrate scope and uses an inexpensive and non-toxic catalyst. Copyright © 2013 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article
Keywords: carbon–carbon cross-coupling; organoboronic acid; aryl iodide; Bi(III)
catalyst, solvent, ligand and time were studied. In the initial
investigation, phenyl iodide and phenyl boronic acid were
Introduction
Metal-catalyzed C–C cross-coupling chemistry has been strenu-
chosen as model substrates and the reaction was carried out in
ꢀ
ously developed because of its use in the synthesis of natural
DMSO at 120 C in the presence of BiCl , KOH (as base) and
3
[
1]
products and other biologically active molecules. In particular,
tetramethylethylenediamine (TMEDA) as ligand. Table 1 provides
a preliminary summary of the scope and limitation of the
bismuth-catalyzed cross-coupling reaction. Our initial experi-
ments were focused on the optimization of the catalyst, and
various Bi(III) salts such as BiCl , BiBr , BiI and Bi(NO ) .5(H O)
2
2
sp -sp cross-couplings have had a great impact on drug
research and development and the new strategies have
[
2]
transformed pharmaceutical research. In fact, today metal-
catalyzed coupling reactions have become a reliable and
indispensable tool for the synthesis of pharmaceuticals and
3
3
3
3 3
2
were used. Results revealed that BiCl (10 mol%) was found to
3
[
3–6]
building blocks for natural products synthesis.
palladium-catalyzed cross-coupling reactions are unparalleled
In particular,
be the most effective catalyst, which afforded 80% coupled prod-
uct (Table 1, entry 2). Among the various bases, KOH (2 equiv.)
provided the best results in this reaction (Table 1, entry 2). When
3 equiv. KOH was used, the yield drops to 70% and the increased
base concentration reduced the yield. This may be due to the
generation of other reaction products upon increasing the KOH
concentration. The effect of ligand on the coupling reaction
was studied using different nitrogen-based ligands (L1–L4
and neutral L5). The results have shown that the 10 mol% L3
(TMEDA) was the most efficacious ligand for the coupling
reaction (Table 2, entry 3).
[
7–23]
because of their spectacular catalytic activity and selectivity.
Over the last three decades, the Suzuki coupling reaction has
become unarguably the most efficient method for the C-C bond
formation. This discovery was honored by awarding the Nobel Prize
[24]
in Chemistry in 2010.
In subsequent developments, various inexpensive and
environmentally benign catalysts have been developed for C–C
cross-coupling reactions. In this regard, transition and non-
[
25–27]
[28]
[29–34]
transition metals such as copper,
cobalt,
iron,
[34–38]
[39]
[40]
[41–44]
nickel,
zinc,
indium,
solid supported catalyst
have been used for C–C cross-coupling
To analyze the effect of solvent, the reactions were carried out
in different solvents such as CH NO , CH CN, THF, 1,4-dioxane,
[
45–49]
and nano particles
3
2
3
reactions. Notably, bismuth(III) halides have drawn significant
attention during the last three decades as reagents that are
inexpensive, relatively non-toxic, environmentally benign and
DMF, DMSO, N-methyl-2-pyrrolidone (NMP) and toluene. It was
found that the reaction proceeded very well in DMSO and DMF
and provided good yields; in fact, a better yield was obtained in
the case of DMSO (Table 1, entry 2 vs. 7). Furthermore, polar aprotic
NMP provided only 60% desired product (Table 1, entry 13). In the
case of toluene the yield was very poor (Table 1, entry 9). To confirm
whether in the presence of KOH DMSO plays any crucial role in the
[
50–54]
fairly insensitive to moisture.
These have been explored as
efficient catalysts for various organic transformations, such as
[
55]
[56]
[57]
oxidation, allylation, Mannich reaction, epoxide-opening
[
58]
[59–61]
reactions
and Diels–Alder reactions.
Our continued
[
62,63]
interest in bismuth chemistry have led us to investigate the
coupling reaction,
the reaction was carried out in the absence
catalytic activity of bismuth(III) compounds towards C–C cross-
coupling reaction. Herein we report the BiCl -catalyzed
3
cross-coupling reaction between organoboronic acids and
aryl iodides.
*
Correspondence to: Debashis Chakraborty, Department of Chemistry, Indian
Institute of Technology Madras, Chennai-600 036, Tamil Nadu, India. Email:
dchakraborty@iitm.ac.in
Results and Discussion
†
Summer intern from Indian Institute of Science Education and Research,
Bhopal, India.
C–C Cross-Coupling Reaction
To develop an optimal catalytic system for the C–C cross-coupling,
various reaction parameters such as effect of temperature,
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600
036, Tamil Nadu, India
Appl. Organometal. Chem. 2013, 27, 519–522
Copyright © 2013 John Wiley & Sons, Ltd.

P. Malik et al.
Table 1. Optimization of reaction conditions for C–C coupling
▪
a
b
Entry
Base
Bi(III) catalyst
Solvent
DMSO
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
NaOH
KOH
BiCl
BiCl
3
30
27
29
33
31
35
27.5
34
40
32
33
35
29
27
27
27
27
27
76
80
70
64
67
62
77
50
20
53
50
52
60
52
55
45
5
3
DMSO
DMSO
KO-t-Bu
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
3
3
3
3
3
3
3
3
3
3
3
K
2
CO
CO
CO
3
DMSO
Cs
Na
2
3
DMSO
2
3
DMSO
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
—
DMF
1,4-Dioxane
Toluene
10
11
12
13
14
15
16
17
18
CH
CH
3
NO
CN
2
3
THF
NMP
BiBr
BiI
Á5(H
3
DMSO
DMSO
DMSO
DMSO
DMSO
3
Bi(NO
3
)
3
2
O)
—
BiCl
3
—
a
Monitored using TLC.
b
Isolated yield after column chromatography of the crude product.
Table 2. Optimization of ligand for C–C coupling
a
Entry
Base
catalyst
Ligand
Time (h)
Yield (%)
1
2
3
4
5
KOH
KOH
KOH
KOH
KOH
BiCl
BiCl
3
L1
L2
L3
L4
L5
27
27
27
27
27
60
61
80
72
47
3
BiCl
3
BiCl
BiCl
3
3
a
Isolated yield after column chromatography of the crude product.
of BiCl (Table 1, entry 17) and only 5% coupled product was
were used. We have observed that the electron-donating
substrates afford product in a short time with good yields as
compared to the electron-withdrawing substrates (Table 3,
entries 2–6 vs. entries 8 and 9).
The kinetics of the coupling of phenyl boronic acid and phenyl
iodide were studied. High-pressure liquid chromatography
(HPLC) was used to determine the various starting materials
3
obtained. In the controlled experiment, when BiCl was used in
3
the absence of KOH, the desired product was not observed (Table 1,
entry 18). Furthermore, other Bi(III) salts as catalyst resulted in much
lower yield.
After the optimized reaction conditions were determined, to
extend the substrate scope of the protocol various aryl iodides
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Copyright © 2013 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2013, 27, 519–522

Bi(III)-catalyzed Suzuki coupling
3
Table 3. BiCl -catalyzed C–C coupling of organoboronic acid and aryl iodides
a
b
Entry
R
1
R
2
Time (h)
Yield (%)
Characterization ref.
1
2
3
4
5
6
7
8
9
H
H
27
24
25
25
28
27.5
29
32
35
29
28
29
30
35
40
35
80
81
80
81
80
79
79
78
77
80
82
81
80
79
80
79
[64]
[64]
[65]
[65]
[64]
[64]
[65]
[65]
[66]
[64]
[64]
[65]
[65]
[65]
[66]
[66]
Me
H
H
H
H
H
H
H
H
2 5
C H
3 3
C(CH )
2-OMe
4-OMe
Cl
F
COOH
10
11
12
13
14
15
16
H
OMe
Me
H
H
CF
3
H
2-Naphthyl-B(OH)
2
2-Naphthyl-I
2-Pyridyl-I
H
H
H
CN
a
Monitored using TLC.
b
Isolated yield after column chromatography of the crude product.
0
0
0
0
0
0
0
0
0
0
.45
.40
.35
.30
.25
.20
.15
.10
.05
.00
-0.6
-0.8
C H -C H
6
5
6
5
Y = -0.1556 + 2.0702 X
R = 0.9417
C H I
6
5
-
-
-
-
-
-
-
1.0
1.2
1.4
1.6
1.8
2.0
2.2
0
5
10
15
20
25
30
-1.0
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
Time (h)
log10 C
Figure 1. Concentration versus time plot for the BiCl
coupling reaction of phenyl iodide and phenyl boronic acid.
3
-catalyzed
Figure 2. van’t Hoff differential plot for the BiCl3 catalyzed coupling
reaction of phenyl iodide and phenyl boronic acid.
À
and product present as a function of time. The concentration Conclusions
versus time plot shows the disappearance of aryl iodide and
We have demonstrated a simple method for the carbon–carbon
the appearance of the coupled product with time. The van’t Hoff
differential method was used to determine the order (n) and rate
constant (k) (Fig. 1).
At different concentrations, the rate of the reaction was calcu-
lated by estimating the slope of the tangent at each point on the
concentration curve. From these data, log10(rate ) versus log10
cross-coupling reactions between organoboronic acid and aryl
iodide. The procedure may be attractive from an environmental
point of view.
Experimental
(concentration) was plotted (Fig. 2) and the order (n) and rate
constant (k) were obtained from the slope of the line and its in-
tercept on the log10 (rate) axis. From these figures it is clear that
General Considerations
the reaction proceeds with second-order kinetics (n ꢁ 2) and the
All the aryl halides and boronic acids were purchased from Aldrich
and used as received. All the solvents were purchased from
À1 À1
rate constant is 0.699 l mol
h .
Appl. Organometal. Chem. 2013, 27, 519–522
Copyright © 2013 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

P. Malik et al.
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Ranchem, India, and purified using standard methods. The products
1
13
are characterized by recording H and C NMR using a Bruker
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Waters HPLC instrument fitted with a Waters 515 pump and a
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To a suspension of boronic acid (1.2 mmol) and BiCl
DMSO, aryl iodide (1 mmol) was added, followed by TMEDA
3
(10 mol%) in
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10 mol%) and KOH (2 equiv.). The reaction mixture was heated
ꢀ
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layer chromatography (TLC). The reaction mixture was extracted
repeatedly with ethyl acetate. All the volatile organics were
removed under reduced pressure. The crude product was
purified using column chromatography. The spectral data of
the various products matched with the available literature
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Supporting information may be found in the online version of
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