Palladium-catalyzed desulfitative cross-coupling of arylsulfinates with arylboronic acids

Article abstract of DOI:10.1039/c4ra07455f

Palladium (Pd)-catalyzed desulfitative cross-coupling reactions of sodium arylsulfinates with a wide variety of arylboronic acids were achieved in good to excellent yields under simple aerobic conditions. These catalytic reactions could be accelerated by addition of a catalytic amount of Cu(ii) salts as co-catalyst. Moreover, these reactions were tolerant to all of the tested functional groups, making them attractive alternatives to the traditional cross-coupling reactions. This journal is

Full text of DOI:10.1039/c4ra07455f

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Palladium-catalyzed desulfitative cross-coupling of
arylsulfinates with arylboronic acids†
Cite this: RSC Adv., 2014, 4, 57923
a
b
a
c
a
a
Kai Cheng, Hai-Zhu Yu, Baoli Zhao, Sai Hu, Xian-Man Zhang and Chenze Qi*
Palladium (Pd)-catalyzed desulfitative cross-coupling reactions of sodium arylsulfinates with a wide variety
of arylboronic acids were achieved in good to excellent yields under simple aerobic conditions. These
catalytic reactions could be accelerated by addition of a catalytic amount of Cu(II) salts as co-catalyst.
Moreover, these reactions were tolerant to all of the tested functional groups, making them attractive
alternatives to the traditional cross-coupling reactions.
Received 22nd July 2014
Accepted 17th October 2014
DOI: 10.1039/c4ra07455f
www.rsc.org/advances
4
1
b). Aryldiazonium salts could also be employed as the elec-
Introduction
trophilic partners for the Pd-catalyzed Suzuki-type cross-
Palladium (Pd)-catalyzed coupling has been demonstrated as a coupling reactions with the release of nitrogen gas (Scheme
5
useful reaction for construction of carbon–carbon chemical 1c). Recently, the decarboxylative cross-coupling reactions
1
bonds in synthetic organic chemistry. For example, the Pd- using the stable and cheap carboxylic acids (or their salts) had
catalyzed cross-coupling of nucleophilic organoboron donors, received much attention as substrates for various coupling
2
6
i.e. the Suzuki cross-coupling, is known as one of the most reactions. For example, Liu and his co-workers rst reported
common synthetic reactions for ne chemicals, pharmaceuti- the synthesis of the biaryls through the Pd-catalyzed decarboxy-
cals and natural products.
lative coupling reactions of aryl carboxylic acids with arylbor-
Aromatic halides were oen employed as the electrophilic onic acids via the C–C bond cleavage (Scheme 1d). However,
7a
reagents for the Pd-catalyzed Suzuki cross-coupling reactions these cross-coupling reactions were catalyzed using 20 mol% of
3
ꢀ
via the C–X bond cleavage (Scheme 1a). Aryl tosylates/mesylates the Pd(TFA) catalyst together with excessive Ag CO at 120 C.
2
2
3
were found as useful electrophiles for the Pd-catalyzed Suzuki– Clearly, it is still desirable to perform these cross-coupling
Miyaura coupling reactions via the C–O bond cleavage (Scheme reactions with less catalyst and oxidants under milder reac-
tion conditions.
The C–S bond cleavage has been shown as an attractive
8
approach for the Pd-catalyzed cross-coupling reactions. Vogel
9a
et al. rst reported the Pd-catalyzed Suzuki-type cross-
couplings of arylsulfonyl chlorides with arylboronic acids in
moderate to good coupling yields (48–92%). The carbene
ligands and bases were shown to be essential for the trans-
formation, and the applications of the arylsulfonyl chlorides
were limited due to the formation of hydrochloride acid (HCl)
by moisture. Interestingly, sodium arylsulnates were also
reported as the coupling partners for the Pd-catalyzed desul-
10,11
tative reactions.
Moreover, the related reaction conditions
were found much milder than those reported for the corre-
1
2
Scheme 1
sponding aryl carboxylic acids. In the present paper, we would
like to report the Pd-catalyzed desultative coupling reactions
of sodium arylsulnates with arylboronic acids to produce
various biaryls with Cu(II) salts as co-catalyst under mild aerobic
conditions (Scheme 1e, this work).
a
Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process,
Shaoxing University, Shaoxing, 312000, China. E-mail: qichenze@163.com; Fax:
+
86-575-88345681; Tel: +86-575-88345681
b
Department of Polymer Science and Engineering, University of Science and Technology
Beijing, Beijing 100083, China
c
Results and discussion
College of Materials Science and Chemical Engineering, Ningbo University, Ningbo,
3
†
1
10014, China
Initially, we attempted to apply the optimized conditions of the
desultative Hiyama cross-coupling with arylsulnates
Electronic supplementary information (ESI) available. See DOI:
0.1039/c4ra07455f
10e
to
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examine the PdCl
2
-catalyzed cross-coupling reaction of sodium Table 2 Screening of oxidants for the desulfitative cross-coupling
reaction of sodium 4-methylbenzenesulfinate with phenylboronic
4-methylbenzenesulnate with phenylboronic acid. The desired
a
acid
cross-coupling product was obtained only at a yield of 29%,
whereas the major product (55%) was derived from the homo-
11a,13
coupling of 4-methylbenzenesulnate (Table 1, entry 1).
Similar product distributions were obtained when carried out in
DMF and toluene solutions (Table 1, entries 2–3). Interestingly,
the homocoupling products were found negligible when carried
b
b
Entry
Oxidant
CuCl
AgOAc
Oxone
TBHP
DDQ
Yield (%)
Entry
Oxidant
Cu(OTf)
Cu(acac)
CuBr2
Cu(TFA)
Cu(OAc)
Cu(OAc)
Yield (%)
3
out in dioxane, THF and CH CN solutions (Table 1, entries 4–6).
There was no much improvement for the cross-coupling yields
when carried out in the mixed solvent of DMSO with acetone,
toluene and methanol, respectively (Table 1, entries 10–12).
However, no homocoupling by-product was found in the mixed
solvent of DMSO with dioxane, THF and CH CN. Most inter-
3
estingly, the cross-coupling product could be noticeably
improved (Table 1, entries 7–9). Nevertheless, the mixture of
3
DMSO and CH CN (1 : 1, v/v) was determined as the optimum
solvent system for the cross-coupling, which was then chosen
for the subsequent studies.
1
2
3
4
5
6
2
92
75
66
77
69
80
7
8
9
10
11
12
2
58
86
81
90
93
2
2
2
c
O
2
2
92
a
Reaction conditions: sodium 4-methylbenzenesulnate (0.50 mmol),
phenylboronic acid (0.60 mmol), PdCl
mmol), DMSO–CH
c
2
(5.0 mol%), oxidant (0.50
ꢀ
3
CN (1 : 1, v/v) (2.0 ml) at 90 C for 2.0 hours.
b
Isolated desultative coupling yields. 0.05 mmol Cu(OAc)
2
was
added.
Because oxidant is required to regenerate the oxidized Pd(II)
species from the reductive Pd(0) species to complete the cata-
lytic cycle, we tested various oxidizing reagents including coupling yield was obtained by addition of a catalytic amount
Cu(OAc) , AgOAc, oxone, TBHP (tert-butyl hydroperoxide), DDQ (10 mol%) of the Cu(OAc) salt (Table 2, entry 12).
2,3-dichloro-5,6-dicyano-1,4-benzoquinone) and O
Next, we turned our attention to screen the palladium cata-
2
2
(
2
. Cu(OAc)
2
was found as the best among the screened oxidants for the Pd- lysts for the model desultative cross-coupling reaction in the
catalyzed desultative cross-coupling reactions (Table 2, entries presence of 10 mol% Cu(OAc)2 co-catalyst and the related
1–6). Additional Cu(II) salts were also screened and the related results were summarized in Table 3. Examination of entries 2
cross-coupling results were included in Table 2 for comparison and 3 of Table 3 shows that the PdI - and Pd(OAc) -catalyzed
2
2
(
Table 2, entries 7–11). Clearly, the highest desultative reactions afforded the cross-coupling products in 87 and 86%
2
+
yields, respectively. Chelation of the Pd species with different
ligands did not improve the catalytic activities (Table 3, entries
4
–7). As expected, relatively lower desultative coupling yields
Table 1 Solvent dependence for the Pd-catalyzed desulfitative cross-
coupling reaction of 4-methylbenzenesulfinate with phenylboronic
acid
were obtained for the Pd(0) catalyzed reactions (Table 3, entries
8–9). Nevertheless, no cross-coupling products were found by
addition of the Ru and Rh catalysts (Table 3, entries 10–11).
a
2
Taken together all of these results, we believed that PdCl was
the most efficient palladium catalyst for the desultative cross-
coupling reactions (Table 3, entry 1).
We suspected that the atmospheric oxygen might be
involved in the oxidative desultative cross-coupling reactions
because the cross-coupling yields (92%) were much higher than
b
b
b
Entry
Solvent
A (%)
B (%)
C (%)
the Cu(OAc)
esis, we examined the PdCl
2
amount (10 mol%). In order to test this hypoth-
-catalyzed desultative cross-
2
1
2
3
4
5
6
7
8
9
DMSO
DMF
Toluene
Dioxane
THF
CH CN
3
DMSO/dioxane
DMSO/THF
29
26
10
31
25
26
70
67
78
22
25
31
55
43
6
—
—
28
—
—
—
—
—
—
—
26
—
coupling reaction of sodium 4-methylbenzenesulnate with
phenylboronic acid under different reaction conditions. No
cross-coupling product was detected in the absence of the
—
—
—
—
—
—
17
19
14
copper co-catalyst [Cu(OAc) ] under nitrogen atmosphere. The
2
cross-coupling product yield was found to be only about 15% in
the presence of 10 mol% Cu(OAc) under nitrogen gas protec-
2
DMSO/CH
DMSO/acetone
DMSO/toluene
3
CN
tion (eqn (2)). However, the cross-coupling product was isolated
with a decent yield of 80% when the reaction was performed
under pure oxygen atmosphere even in the absence of the
1
1
1
0
1
2
3
DMSO/CH OH
copper co-catalyst [Cu(OAc)
Reaction conditions: sodium 4-methylbenzenesulnate (0.50 mmol), oxygen and 10 mol% of Cu(OAc)
2
], indicating that the atmospheric
were both essential for the Pd-
a
2
phenylboronic acid (0.60 mmol), PdCl
2
(5.0 mol%), mixed solvent of
b
catalyzed desultative cross-coupling reactions of arylsulnates
with arylboronic acids.
ꢀ
DMSO and CH
3
CN (2.0 ml, v/v ¼ 1 : 1) at 90 C for 2.0 hours. Yield
of A, B or C was obtained from the GC-MS analysis using naphthalene
as the internal standard.
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Table 3 Effects of the transition metal catalysts on the desulfitative Table 4 Pd-catalyzed desulfitative coupling of arylsulfinates with
a
cross-coupling reaction of 4-methylbenzenesulfinate with phenyl- arylboronic acids
boronic acid
a
b
Entry
Catalyst
Yield (%)
b
Entry
R
1
R
2
Yield (%)
1
2
3
4
5
6
7
8
9
PdCl
PdI
Pd(OAc)
Pd(dppf)Cl
PdCl (PPh
Pd(PCy Cl
Pd(PhCN)
2
92
87
86
73
75
48
89
55
51
—
—
1
2
3
4
5
6
7
8
9
C
C
C
C
C
C
C
C
C
C
C
6
6
6
6
6
6
6
6
6
6
6
H
H
H
H
H
H
H
H
H
H
H
5
5
5
5
5
5
5
5
5
5
5
4-CH
3-CH
2-CH
4-NO
3-NO
2-ClC H
6 4
2-Naphthyl
1-Naphthyl
4-ClC
4-BrC
4-OHCC
4-NH C H
4-HOC
3
3
3
2
2
OC
OC
OC
6
6
6
H
H
H
4
4
4
93
91
84
88
91
85
94
84
93
90
86
82
87
91
94
89
92
88
89
86
90
91
87
93
90
84
62
79
2
2
2
C
C
6
H
H
4
2
3
)
3
6
4
3 2
)
2
2
Cl
2
Pd(PPh
3
)
4
Pd (dba)
2
3
6 4
H
1
1
0
1
3 3
RhCl(PPh )
1
1
0
1
6
H
4
[RuCl (p-cymene)]
2
2
6
H
4
a
12
C6H5
Reaction conditions: sodium 4-methylbenzenesulnate (0.5 mmol),
2
6
4
phenylboronic acid (0.6 mmol), catalyst (5.0 mol%), co-catalyst 13
C
6
H
5
6
H
4
ꢀ
[
Cu(OAc)
2
] (10 mol%), DMSO–CH
3
CN (1 : 1, v/v) (2.0 ml) at 90 C for 14
4-CH
4-C H C H
4-ClC
3
OC
6
H
4
6 5
C H
C6H5
b
2
.0 hours. Isolated desultative cross-coupling yields.
15
2
5
6
4
1
1
1
1
2
2
2
2
2
2
2
2
2
6
7
8
9
0
1
2
3
4
5
6
7
8
6
H
4
C
6
C
6
C
6
C
6
C
6
C
6
C
6
C
6
C
6
C
6
C
6
C
6
C
6
H
5
H
5
H
5
H
5
H
5
H
5
H
5
H
5
H
5
H
5
H
5
H
5
H
5
4-BrC
4-FC
4-NO
4-AcC
4-CH
3-CH
2-CH
2-Naphthyl
1-Naphthyl
2-Thiophyl
6 4
H
H
4
6
2
C
6
H
4
6
H
4
3
C
6
C
6
C
6
H
H
H
4
4
4
3
3
1H-Tetrazol-5-yl
Pyridin-2-yl
Scheme 2
a
Reaction conditions: sodium arylsulnate (0.50 mmol), arylboronic
acid (0.60 mmol), Pd(OAc)
CH
desultative coupling yield.
2
(5.0 mol%), Cu(OAc)
2
(10 mol%), DMSO–
ꢀ
b
3
CN (3 : 1, v/v) (2.0 ml) at 90
C for 2.0 hours. Isolated
2
The optimized protocol was also applicable to the PdCl -
catalyzed desultative cross-coupling reactions for other aryl-
sulnates and arylboronic acids as evident from Table 4.
Examination of Table 4 shows that good to excellent isolated
yields were obtained from the Pd-catalyzed desultative cross-
In order to understand the cross-coupling mechanisms, we
coupling reactions for the arylsulnates and arylboronic acids employed the density functional theory (DFT) calculation to
bearing various functional groups including alkyl (Table 4, determine the C–SO R bond dissociation enthalpies (BDEs)
entries 15 and 21–24), carbonyl (Table 4, entries 11, 20), alkoxyl using the M06-2X/6-31G(d) basis set. Recently, Dang and Shi
Table 4, entries 1–3 and 14), nitro (Table 4, entries 4–5 and 19) developed this reliable DFT method to calculate the different C–
2
14
(
and halogen (Table 4, entries 6 and 16–18). Interestingly, the SO R BDEs. Some interesting results were summarized for the
2
cross-coupling reactions seem to be insensitive to the steric cross-coupling of the sulnic acid salts and boronic acids [the
15
effects as well as the polarity of the substituents. For example, Cu-catalyzed couplings in Scheme 2a and the Pd (or Pd/Cu)
the desultative cross-coupling yields were similar for both catalyzed desultative couplings in Scheme 2b].
substrates containing the meta or ortho substituent (Table 4,
entries 2, 3, 4, 5, 22 and 23) even with the fused aromatic rings determining step for the intriguing Cu- and Pd-catalyzed
Table 4, entries 7, 8, 24 and 25). The substrates bearing with desultative cross-coupling reactions (Scheme 3a). Interest-
free amine and hydroxyl functional groups also worked well for ingly, the sulnic group tends to be retained for the Cu-
Our focus was to examine the possible pathways of the rate-
(
s
ꢁ1
this cross-coupling reaction (Table 4, entries 11–13). Most catalyzed reaction systems (DH ¼ 38.9 kcal mol , TS-
interestingly, the cross-coupling reaction was also tolerant to SCuOAc), whereas the desultative coupling is more favour-
s
the heterocyclic sulnate salts (Table 4, entries 26–28). 2-Phe- able for the Pd-catalyzed reaction systems (DH ¼ 11.1 kcal
ꢁ
1
nylthiophene, 5-phenyl-1H-tetrazole and 2-phenylpyridine were mol , TS-SPdCl) (Scheme 3c, R ¼ phenyl). Aer carefully
synthesized in moderate to good yields.
examining the possible pathways, we believe that the cross-
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product leads to formation of the reductive Pd(0) species, which
will be oxidized into the oxidative Pd(II) species by Cu(II) to
complete the catalytic cycle as shown in Scheme 4. Cu(I) is then
oxidized by oxygen to regenerate Cu(II) which makes the usage
17
of copper to catalytic cycle.
Conclusions
In summary, we have demonstrated that excellent desultative
cross-coupling yields could be achieved from the PdCl -cata-
2
lyzed reactions of arylsulnates with arylboronic acids under
mild aerobic reaction conditions. The palladium catalyzed
desultative coupling reactions could be further accelerated by
2
addition of a catalytic amount of the co-catalyst Cu(OAc) . The
wide availability of the arylsulnate salts enables this trans-
formation to be an attractive alternative to the cross-coupling
even in the absence of ligands and bases.
Scheme 3 DFT calculation.
Acknowledgements
2
coupling reaction must proceed via a concerted SO dissocia-
The authors acknowledge the nancial support from the
National Natural Science Foundation of China (no. 21402123
and 21202102), the Zhejiang Provincial Natural Science Foun-
dation of China (no. LQ14B020001), and the Science Tech-
nology Project of Shaoxing City (no. 2013014017).
tion mechanism with a four-membered transition state. Release
of the neutral SO molecule is the most favourable pathway to
generate R–[M] for both the Pd- and Cu-catalyzed reaction
systems (Scheme 3b).
The DFT theoretical calculations provided the additional
support for our Pd/Cu-catalyzed desultative cross-coupling
2
mechanism, i.e. the most favourable desulnative step in the Notes and references
2
Pd-catalyzed systems. The strong CSO –[Cu] bond strength was
presumably the main reason for the difficult desulnative step
in the Cu-catalyzed reaction system.
Therefore, the rst step for the Pd-catalyzed desultative
cross-coupling reaction may involve the nucleophilic attack of
1
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