Excellent Suzuki–Miyaura catalytic activity of a new Pd(II) complex with sulfonamide–Schiff base ligand

Article abstract of DOI:10.1002/aoc.3464

A new air-stable Pd(II) complex containing a sulfonamide–Schiff base ligand has been synthesized, characterized and investigated as a catalyst for the Suzuki–Miyaura reactions of aryl halides with arylboronic acids. Theoretical calculations (B3LYP) and spectroscopic evidence suggest that the sulfonamide–Schiff base coordinates to the Pd centre through sulfonamide nitrogen (?SO₂NH₂) rather than imine (?CH?N). The complex shows excellent cross-coupling activity with aryl bromides in water at room temperature and aryl chlorides in isopropanol at 60°C. Copyright

Full text of DOI:10.1002/aoc.3464

Full paper
Received: 19 October 2015
Revised: 25 December 2015
Accepted: 29 January 2016
Published online in Wiley Online Library: 28 March 2016
(wileyonlinelibrary.com) DOI 10.1002/aoc.3464
Excellent Suzuki–Miyaura catalytic activity of a
new Pd(II) complex with sulfonamide–Schiff
base ligand
a,b
a
c
a
Biplab Banik , Archana Tairai , Pradip K. Bhattacharyya and Pankaj Das *
A new air-stable Pd(II) complex containing a sulfonamide–Schiff base ligand has been synthesized, characterized and investigated
as a catalyst for the Suzuki–Miyaura reactions of aryl halides with arylboronic acids. Theoretical calculations (B3LYP) and spectro-
scopic evidence suggest that the sulfonamide–Schiff base coordinates to the Pd centre through sulfonamide nitrogen (–SO NH )
2 2
rather than imine (–CH¼N). The complex shows excellent cross-coupling activity with aryl bromides in water at room temperature
and aryl chlorides in isopropanol at 60°C. Copyright © 2016 John Wiley & Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web site.
Keywords: Palladium; sulfonamide–Schiff base; Suzuki–Miyaura reaction; water; aryl halides; DFT study
in Pd-catalysed cross-coupling reactions including Suzuki–Miyaura
Introduction
reactions, and some efficient catalytic systems have been devel-
[
10,11]
[11]
Palladium (Pd)-catalysed Suzuki–Miyaura cross-coupling reactions
of aryl halides with arylboronic acids have been established as
one of the most versatile methods for the construction of C–C
oped so far.
However, except for a few recent cases, the ma-
jority of Schiff base-derived catalytic systems failed to promote aryl
chlorides as substrates. Thus, in order to expand the scope of Schiff
base ligands further in Suzuki–Miyaura reactions, herein we report
the synthesis and catalytic activity of a new Pd(II) complex contain-
ing a sulfonamide–Schiff base as ligand. Sulfonamide–Schiff bases
are a unique class of compounds that contain both Schiff base
[
1]
bonds in organic synthesis. Like any other homogeneous
catalytic reaction, in the Suzuki reaction also the ligand environ-
ment around the Pd centre holds the key to controlling the efficacy
of a catalytic system. Thus, in the past few years, many attempts
have been made to develop novel Pd complexes with accessible
ligand systems, which can act as highly active catalysts particularly
to deal with inexpensive and readily available aryl chlorides as
(CH¼N) and sulfonamide (SO NH) fragments in the same ligand
2
[
12]
framework. Because of the presence of pharmacologically active
sulfonamide group, this type of compound continues to occupy an
important position in medical chemistry including showing
[2]
substrates. Significant advances have been achieved in develop-
ing efficient catalytic systems for aryl chlorides with notable
[
12a]
[12b]
anticancer,
activities.
anti-inflammatory
and
antimicrobial
[
3]
[12d,12e]
ligands such as Buchwald’s biaryl phosphines, Kwong’s P,N-
The sulfonamide–Schiff base 4-[(benzylidene)
[4]
[5]
donor ligands, Fu’s tertiary phosphines, Nolan’s N-heterocyclic
amino]benzenesulfonamide (L1) was first reported by Ayad et al.
[6]
[7]
[8]
[13]
carbenes, Sarkar’s indole-based phosphines and others.
However, the majority of these systems suffer from limitations like
in 1991; however, the coordination chemistry and catalytic po-
tentials of sulfonamide–Schiff bases have rarely been studied, de-
[
4,7]
high reaction temperatures (100–130°C),
use of environmen-
spite the fact that these ligands contain at least two potential
[
14]
tally undesirable solvents (toluene, dimethylformamide (DMF),
donor nitrogen sites. Nevertheless, there is one report of the syn-
thesis of a Pd complex with a sulfonamide–Schiff base derivative
that showed excellent catalytic activity for alcohol oxidation reac-
[3–5]
dioxane),
employment of air- and moisture-sensitive phos-
[3,5]
phines as ligands,
high palladium loadings (up to 4 mol%),
[7]
[15]
etc. Thus, the advantages associated with excellent activities of
such systems are often negated by the high cost and environmen-
tal impacts associated with the uses of such phosphines, high
metal loadings and undesirable organic solvents. Therefore, from
the practical viewpoint, the development of new phosphine-free
catalytic systems for Suzuki–Miyaura reactions especially using
environmentally benign reaction media under mild conditions is
still considered to be a great challenge.
tion. However, to the best of our knowledge, there is no report
on the use of sulfonamide–Schiff bases in the Suzuki–Miyaura
cross-coupling reaction. Thus, as a part of our work on phosphine-
free catalytic systems, herein we report a new Pd complex
*
Correspondence to:Pankaj Das, Department of Chemistry, Dibrugarh University,
Over the past few decades, Schiff bases have been playing an im-
portant role as phosphine-free ligands in catalysis because of their
easy synthesis, high stability and air- and moisture-insensitive
properties. Like phosphines, the steric and electronic properties
of Schiff bases can be easily tuned by properly selecting condens-
ing partners. Hence, Schiff bases have been vigorously explored
Dibrugarh – 786004, Assam, India. E-mail: pankajd29@yahoo.com
a Department of Chemistry, Dibrugarh University, Dibrugarh 786004, Assam, India
b Department of Chemistry, Tinsukia College, Tinsukia 786125, Assam, India
c Department of Chemistry, Arya Vidhyapith College, Guwahati, Assam, India
[9]
Appl. Organometal. Chem. 2016, 30, 519–523
Copyright © 2016 John Wiley & Sons, Ltd.

B. Banik, A. Tairai, P. K. Bhattacharyya and P. Das
containing sulfonamide–Schiff base that shows excellent activity
for the Suzuki reactions of aryl halides under mild conditions.
Experimental
Materials and methods
Scheme 1. Synthesis of Pd complex 1 with sulfonamide–Schiff base ligand.
Pd(OAc)
2
and the starting material sulfanilamide were purchased
+
due to [M + H] at m/z = 485 with a relative intensity of 10%. For
from Acros Organics. The substrates used in the Suzuki–Miyaura re-
actions were purchased from Sigma-Aldrich, Spectrochem and
Rankem. All other chemicals and solvents of analytical grade were
purchased from various Indian firms. The solvents were distilled
and dried prior to use. Elemental analyses (C, H, N) were carried
out using a PerkinElmer 2400 Series II analyser. The mass spectrum
of the complex was obtained with a Waters ZQ-4000 ESI/MS. Infra-
Schiff bases, the analysis of IR spectra clearly indicates whether they
are coordinated or not, by observing the changes in the νC¼N
stretching frequency. The νC¼N stretching in complex 1 appears at
ꢀ1
1
622 cm which is exactly the same as that of the free ligand sug-
gesting that the Schiff base imine is not involved in coordination.
On the other hand, upon complexation, a significant shift of ν
NH2
ꢀ1
stretching from 3296 to 3240 cm and νNH2 bending from 1579
ꢀ
1
red (IR) spectra (250–4000 cm ) were recorded in KBr using a
ꢀ1
to 1552 cm is observed which substantiates the participation of
1
Shimadzu (Prestige-21) spectrophotometer. H NMR spectra were
sulfonamide (–SO NH ) nitrogen in coordination with Pd. This fact
2
2
recorded with a Bruker Avance II 400 MHz spectrometer.
1
is further corroborated by H NMR spectra. Most notable is the
downfield shift of the sulfonamide proton singlet from 5.70 to
6.90 ppm upon coordination. A similar downfield shift of amine
proton signal upon coordination was reported for other Pd com-
Synthesis of Pd catalyst
The sulfonamide–Schiff base ligand L1 was prepared following a re-
[
15]
[13]
plexes with aromatic sulfonamides. The imine proton signal ap-
pears almost at the same position as that of the free ligand.
ported procedure. A solution of ligand L1 (0.34 g, 1.33 mmol) in
5 ml of acetonitrile was added dropwise to a solution of Pd(OAc)
0.30 g, 1.33 mmol) in 10 ml of acetonitrile. After refluxing the reac-
1
2
(
tion mixture for 4 h, the yellowish precipitate was filtered. The res-
idue was washed with hexane and finally complex 1 was obtained
Density functional study
as a light yellow solid. Yield: 82%. Anal. Calcd for C17
H
18
N
2
O
6
SPd
Due to the insolubility of the complex in commonly used solvents,
we are unable to develop diffraction-quality crystals for X-ray study,
and hence we have carried out a geometry optimization study for
complex 1 using gas-phase density functional theory (DFT) with
B3LYP/6-31+G(d) level of theory. Both the theoretically possible
imine- and amine-bonded structures were considered for optimiza-
tion and the optimized structures are shown in Figs. 1(a) and (b),
(
%): C, 42.11; H, 3.74; N, 5.77. Found (%): C, 42.07; H, 3.72; N, 5.74.
+
+
MS-ESI (DMSO, m/z): 485 [M + H] , 406 [M ꢀ Ph ꢀ H] . Selected IR
ꢀ
1
2
frequencies (cm , KBr): 1622 (νC¼N: imine), 1552 (νN–H(bend): NH ),
3
1
3
240 (νN–H(sym): NH
2
), 1321 (νS¼O(asym): SO
2
), 1134 (νS¼O(sym): SO
589 (νCOO: acetate). H NMR (400 MHz, DMSO-d , δ, ppm): 2.12 (s,
H, CH ), 2.57 (s, 3H, CH
), 8.63 (s, 1H, CH¼N), 7.34–7.96 (m, 9H,
).
2
)
1
6
3
3
Ph), 6.90 (s, 2H, NH
2
General procedure for Suzuki–Miyaura reaction
A 50 ml round-bottom flask was charged with a mixture of aryl ha-
lide (0.5 mmol), arylboronic acid (0.55 mmol), K CO (1.5 mmol) and
2
3
Pd catalyst (0.2 mol% for aryl bromide or 1 mol% for aryl chloride)
and the mixture was stirred for required times at room temperature
i
in water (6 ml) for aryl bromides or at 60°C in PrOH (6 ml) for aryl
chlorides. After completion, the reaction mixture was diluted with
water (20 ml) and extracted with ether (3 × 20 ml). The combined
extract was washed with brine (3 × 20 ml) and dried over Na SO .
2 4
After evaporation of the solvent under reduced pressure, the resi-
due was chromatographed (silica gel, ethyl acetate–hexane, 1:9)
to obtain the desired product. The products were confirmed by
1
comparing the H NMR and mass spectral data with those of au-
thentic samples.
Results and discussion
Synthesis and characterization of catalyst
2
A new Pd complex (1) has been prepared by reacting Pd(OAc) with
ligand L1 in 1:1 molar ratio (Scheme 1). Complex 1 was isolated as a
light yellow solid and its identity was confirmed using elemental
1
analyses and ESI mass, IR and H NMR spectroscopies. The complex
is insoluble in almost all commonly used solvents except DMSO.
The ESI mass spectrum of complex 1 shows a molecular ion peak
Figure 1. Optimized lowest-energy structure of (a) imine-bonded and (b)
amine-bonded Pd complex with sulfonamide–Schiff base with the atom
labelling.
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2016, 30, 519–523

Excellent Suzuki–Miyaura activity of a new palladium catalyst
respectively. Slightly distorted square planar geometries around Pd
centres are observed for both the structures. The optimized struc-
tural parameters, bond lengths and angles for the two possible
bonding modes of the complex obtained from DFT calculations
are listed in the supporting information (Tables S1 and S2). On
the basis of total energy calculation, the amine-bonded structure
considered only protic solvents as these are considered to be envi-
[
17]
ronmentally benign from green chemistry perspectives. The re-
actions were performed using 0.2 mol% of catalyst at room
temperature in the absence of additives, as these conditions were
found to give the best results with one of our recently reported
[11]
Schiff base-derived Pd catalysts. The results are summarized in
Table 1. We were delighted to observe that water is an excellent sol-
vent for our catalytic system and quantitative formation of 4-
methoxybiphenyl is obtained in just 2 h (Table 1, entry 1). It may
be noted that during the past few years, water has attracted signif-
icant attention as a solvent in Suzuki–Miyaura reactions mainly be-
ꢀ
1
(Fig. 1(b)) is found to be slightly more stable (ca 5.34 kcal mol )
than the imine-bonded structure (Fig. 1(a)). Thus, the computa-
tional results further corroborate the spectroscopic findings that
amine–Pd is the most likely mode of bonding in complex 1. The cal-
culated value of Pd–N distance (2.13 Å) is very close to that of some
related sulfonamide complexes for which X-ray structures are
cause of its cost effectiveness and environmentally benign
[
16]
[11,18]
known (Pd–N distance of 2.04–2.07 Å).
Catalytic Activity
nature.
Compared with our previously reported catalytic
[
11]
system, the present catalytic system is much superior as it re-
quires much less time to produce similar results. In addition to wa-
To study the efficacy of our complex as a catalyst for the Suzuki–
Miyaura reaction, we chose 4-bromoanisole and phenylboronic
acid as model substrates. For solvent optimization study, we
i
ter, other alcoholic solvents like EtOH and PrOH also give
comparable results (entries 2 and 4). It is interesting to note that
a
Table 1. Suzuki–Miyaura cross-coupling reactions of various aryl/heteroaryl bromides with arylboronic acids at room temperature
Entry
RBr
R′
Solvent
Base
Time
h)
Yield
b
(
(%)
1
2
3
4
5
6
4-OCH
4-OCH
4-OCH
4-OCH
4-OCH
4-OCH
3
C
6
H
4
Br
Br
Br
Br
Br
Br
C
6
H
5
H
2
O
K
2
CO
CO
CO
CO
CO
CO
3
2
99
99
80
98
30
99
3 6
C
H
4
C
6
H
5
EtOH
K
2
3
3
3 6
C
H
4
C
6
H
5
MeOH
K
2
3
12
2
i
3 6
C
H
4
C
6
H
5
PrOH
K
2
3
3 6
C
H
4
C
6
H
5
n-BuOH
K
2
3
24
1
i
3 6
C
H
4
C
6
H
5
PrOH–
K
2
3
2
H O
7
3 6 4
4-OCH C H Br
C H
6 5
EtOH–
K CO
2 3
1
98
2
H O
8
9
4-OCH
4-OCH
4-OCH
4-OCH
4-OCH
4-OCH
4-CH
4-CHOC
4-NO
3
C
6
H
4
Br
Br
Br
Br
Br
Br
C
6
H
5
H
2
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
K
2
CO
3
2
99
3 6
C
H
4
C
6
H
5
H
2
NaOH
KOH
3
98
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
3 6
C
H
4
C
6
H
5
H
2
10
5
95
3 6
C
H
4
C
6
H
5
H
2
MgCO
Na CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
96
3 6
C
H
4
C
6
H
5
H
2
2
3
8
99
3 6
C
H
4
C
6
H
5
H
2
K
2
3
2
95
3
C
6
H
4
Br
C
6
H
5
H
2
K
2
3
2
97
6
H
4
Br
Br
C
6
H
5
H
2
K
2
3
3
98
c
c
2
C
6
H
4
C
6
H
5
H
2
K
2
3
12/6
6
45/92
99
C H
6 5
Br
C
6
H
5
H
2
K
2
3
4-OCH
4-OCH
4-OCH
2-CHOC
2-CH
2,5-OCH
3
C
6
H
4
Br
Br
Br
Br
4-ClC
4-CH
3-NO
6
H
4
H
2
K
2
3
5
95
3
C
6
H
4
3
C
6
H
4
H
2
K
2
3
3
98
3
C
6
H
4
2
C
6
H
4
H
2
K
2
3
12
12
6
20
c
c
6
H
4
C
6
H
5
H
2
K
2
3
64/88
62/92
85
3 6
C
H
4
Br
Br
C
6
H
5
H
2
K
2
3
3
C
6
H
3
C
6
H
5
H
2
K
2
3
6
d
5-Bromopyrimidine
2-Bromo-
C
6
H
5
H
2
K
2
3
12
12
46/88
34/91
d
C
6
H
5
H
2
K
2
3
3-methylthiophene
a
Reaction conditions: arylbromide (0.5 mmol), arylboronic acid (0.6 mmol), base (1.5 mmol), solvent (6ml).
b
Isolated yields. Yields are average of two runs.
c
PrOH–H
2
O (1:1) used as solvent.
d
T = 50°C.
Appl. Organometal. Chem. 2016, 30, 519–523
Copyright © 2016 John Wiley & Sons, Ltd.
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B. Banik, A. Tairai, P. K. Bhattacharyya and P. Das
product formation becomes slightly faster when neat water, neat
heteroaryl halides are usually very difficult substrates to activate in
Suzuki–Miyaura reactions and often they give low yields. However,
in our case, heteroaryl bromides such as 5-bromopyrimidine and 2-
i
PrOH or neat EtOH is replaced by mixed aqueous–alcoholic sol-
i
vents such as H
2
O–PrOH (entry 1 or 4 versus entry 6) or H
2
O–EtOH
(
entry 1 or 2 versus entry 7). On evaluating the effects of bases in
bromo-3-methylthiophene under slightly warm conditions give ex-
i
our model reaction, we have screened some commonly available
bases for our model reaction using water as solvent (Table 1, entries
2
cellent yields when PrOH–H O is used as solvent (Table 1, entries
24 and 25).
8
–12). Our study reveals that catalyst 1 can tolerate common bases
Encouraged by our results with aryl bromides, we have extended
the scope of our catalytic system for the cross-coupling reactions of
aryl chlorides using water as reaction medium. Initial coupling
reactions were performed using p-chloronitrobenzene with
phenylboronic as model substrates. Unfortunately, only very poor
yield is obtained when water is used as solvent at a relatively high
temperature of 60°C with 0.2 mol% of catalyst (Table 2, entry 1).
As mentioned earlier, aryl chloride activation is one of the most dif-
ficult tasks in Suzuki reactions and often requires a drastic reaction
and excellent yields are obtained with almost all the bases
screened. However, K CO is found to be the most effective base
as it requires much less time compared to other bases.
Inspired by the initial reactions, we have explored the scope of
our catalyst for several representative coupling reactions with a
range of aryl bromides using water as solvent and K CO as base (
2
3
2
3
Table 1, entries 13–25). Usually, aryl bromides bearing electron-
donating groups (e.g. Me, OMe) and electron-withdrawing groups
[
8b]
(NO , CHO) at para-position couple efficiently with phenylboronic
condition including very high catalyst loading (up to 10 mol%).
2
acid to produce corresponding biaryls in excellent yields (Table 1,
entries 13–16). High yields are also maintained when phenyl-
boronic acid is replaced by other arylboronic acids such as p-
chlorophenylboronic acid (entry 18) or p-tolylboronic acid (entry
On increasing the catalyst loading to 1 mol%, no significant im-
provement is observed when water is used as solvent. However,
changing the solvent from water to PrOH or DMF (Table 2, entries
i
2 and 4) significantly improves the catalytic efficacy, and almost
quantitative conversion of cross-coupling product is obtained.
19). However, m-nitrophenylboronic acid gives only poor yield. A
i
similar observation for m-nitrophenylboronic acid was also noted
From an environmental perspective, PrOH is a superior solvent over
[1]
[17]
i
earlier, although the exact reason for this is not known.
DMF
and, hence, for remaining aryl chloride screening, PrOH
It is worth noting that sterically bulky ortho-substituted aryl bro-
mides such as 2-bromotoluene (entry 22) and 2-bromben-
zaldehyde (entry 21) produce only moderate yields; however, the
yields can be significantly improved by using PrOH as co-solvent
with water in 1:1 proportion. It is important to mention that
was used as solvent (Table 2, entries 8–17). Our study reveals that
aryl chlorides bearing electron-withdrawing groups (entries 8 and
9) or electron-donating groups (entries 11 and 12) at para-position
undergo smooth coupling with phenylboronic acid and afford the
desired biaryl in excellent yields. No major differences in yields
i
a
Table 2. Suzuki–Miyaura cross-coupling reactions of various aryl/heteroaryl chlorides with aryl boronic acids
Entry
RCl
R′
Solvent
O
Base
Time
h)
Yield
b
(
(%)
c
1
2
3
4-NO
4-NO
4-NO
2
C H
6 4
Cl
Cl
Cl
C
6
H
5
H
2
K
2
CO
CO
CO
3
12
8
22/10
i
2
C H
6 4
C
6
H
5
PrOH
K
2
3
98
40
i
2
C H
6 4
C
6
H
5
PrOH–
O (1:1)
K
2
3
12
H
2
4
5
4-NO
4-NO
2
C
6
H
4
Cl
Cl
C
6
H
5
DMF
DMF–
O (1:1)
Glycerol–
K
2
CO
CO
3
12
12
98
50
2 6
C
H
4
C
6
H
5
K
2
3
H
2
6
4-NO
2
C
6
H
4
Cl
C
6
H
5
K
2
CO
3
5
60
2
H O
7
8
9
4-NO
4-NO
4-CHOC
Cl
4-CH
4-OCH
2-OCH
2
C
6
H
4
Cl
Cl
C
6
H
5
Toluene
K
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
12
8
20
96
87
96
98
88
68
88
20
85
81
i
2 6
C
H
4
C
6
H
5
PrOH
K
2
3
i
6
H
4
Cl
C
6
H
5
PrOH
K
2
3
12
6
i
10
11
12
13
14
15
16
17
C H
6 5
C
6
H
5
PrOH
K
2
3
i
3
C
6
H
4
Cl
C
6
H
5
PrOH
K
2
3
6
i
3
C
6
H
4
Cl
Cl
C
6
H
5
PrOH
K
2
3
12
12
12
12
12
6
i
3
C
6
H
4
4-ClC
4-CH
3-NO
4-CH
4-ClC
6
H
4
PrOH
K
2
3
i
3-Chloropyridine
3
C
6
H
4
PrOH
K
2
3
i
4-NO
4-NO
4-NO
2
C
6
H
4
Cl
Cl
Cl
2
C
6
H
4
PrOH
K
2
3
i
2 6
C
H
4
3
C
6
H
4
PrOH
K
2
3
i
2 6
C
H
4
6 4
H
PrOH
K
2
3
a
2 3
Reaction conditions: aryl chloride (0.5 mmol), arylboronic acid (0.6 mmol), K CO (1.5 mmol), solvent (6ml).
b
Isolated yields. Yields are average of two runs.
Reaction performed with 0.2 mol% catalyst.
c
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Appl. Organometal. Chem. 2016, 30, 519–523

Excellent Suzuki–Miyaura activity of a new palladium catalyst
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are observed when phenylboronic acid is replaced by 4-
chloroboronic acid (entry 17) or 4-tolylboronic acid (entry 16). Inter-
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strates that are usually difficult to activate; for instance, sterically
bulky substrate (2-chloroanisole; entry 13) or heteroaryl chloride
3
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reactivity. Good-to-excellent yields of cross-coupling products were
obtained with aryl bromides in water at room temperature and aryl
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chlorides in PrOH under mild conditions (1 mol% catalyst loading,
9484. g)E. G. Bowes, G. M. Lee, C. M. Vogels, A. Decken, S. A. Westcott,
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Acknowledgments
The Department of Science and Technology, New Delhi, is grate-
fully acknowledged for financial support (EMR/2015/000021).
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Table S1: Calculated bond length and bond angles of the imine-
bonded isomer
Table S2: Calculated bond length and bond angles of the amine-
bonded isomer
[
Appl. Organometal. Chem. 2016, 30, 519–523
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