Desulfonative pd-catalyzed coupling of aryl trifluoroborates with arylsulfonyl chlorides

Article abstract of DOI:10.1002/aoc.3504

A Pd-catalyzed cross-coupling of aryl trifluoroborates with arylsulfonyl chlorides has been successfully achieved. This transformation is a new method for the Suzuki–Miyaura-type reaction of aryl trifluoroborates via the cleavage of C? S bond, thus providing an alternative synthesis of biaryls. The reported cross-coupling reactions are tolerant to many common functional groups regardless of electron-donating or electron-withdrawing nature, making these transformations attractive alternatives to the traditional Suzuki–Miyaura coupling approaches. Copyright

Full text of DOI:10.1002/aoc.3504

Full paper
Received: 4 December 2015
Revised: 2 April 2016
Accepted: 10 April 2016
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.3504
Desulfonative pd-catalyzed coupling of aryl
trifluoroborates with arylsulfonyl chlorides
a
b
c
a
Zhen Wei *, Dazhong Xue , Haisheng Zhang and Jinyu Guan
A Pd-catalyzed cross-coupling of aryl trifluoroborates with arylsulfonyl chlorides has been successfully achieved. This transforma-
tion is a new method for the Suzuki–Miyaura-type reaction of aryl trifluoroborates via the cleavage of C– S bond, thus providing an
alternative synthesis of biaryls. The reported cross-coupling reactions are tolerant to many common functional groups regardless
of electron-donating or electron-withdrawing nature, making these transformations attractive alternatives to the traditional
Suzuki–Miyaura coupling approaches. 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: arylsulfonyl chlorides; Pd-catalyzed; Suzuki–Miyaura coupling; aryl trifluoroborates
[
36]
via the cleavage of the C– C bond.
However, the research on
Introduction
another attractive method via the cleavage of the C– S bond –
desulfitative coupling – is still lacking. Cross-coupling reactions
of arylsulfonyl and sulfinate compounds have been well devel-
Transition-metal-catalyzed cross-coupling reactions have been
established as indispensable tools for carbon–carbon bond forma-
tion in modern organic synthesis.
reagents (Suzuki reaction and Suzuki–Miyaura reaction) represent
attractive coupling partners due to their excellent reactivity, ready
availability, relative stability and good functional group compatibil-
[
1–4]
[37,38]
In this area, organoboronic
oped as an efficient synthetic method in recent years.
[
39–50]
[51–64]
Arylsulfonyl chlorides,
arylsulfinates
have been used as desulfonative/desulfitative
and arylsulfonyl
[
65–71]
hydrazides
arylation reagents in the synthesis of biaryls. Although arylsulfonyl
chlorides are inexpensive and readily available compounds and
have been used for many years in industry, they have not been
extended to Pd-catalyzed carbon–carbon bond formation with
organotrifluoroborates.
Herein, we report an effective and practical protocol for the prep-
aration of biaryls from various aryl- and heteroaryl trifluoroborates
with arylsulfonyl chlorides via the breaking of a C– S bond under
conditions that are tolerant of a broad range of functional groups.
[
5–10]
ity when compared to other organometallic reagents.
Unlike
boronic acids, which are susceptible to undesired side reactions,
organotrifluoroborates have proven to be air-, moisture- and
bench-stable reagents. They are generally crystalline and mono-
meric solids, air- and water-stable and easy to handle. The use of
organotrifluoroborates as nucleophiles provides an attractive
method for carbon–carbon bond formation as they are easily acces-
sible and handled, and they show high stability towards moisture
[
11–13]
and air, and produce relatively benign byproducts.
Moreover,
organotrifluoroborates are insensitive to various functional groups
and do not undergo undesirable side reactions even under harsh
reaction conditions. Organotrifluoroborate salts have been well
studied by Molander and others as an alternative to organoboronic
Results and discussion
We employed coupling partners phenyl trifluoroborate and 4-
methylphenylsulfonyl chloride as model substrates to identify reac-
tion conditions. The optimized conditions for desulfonative cou-
[14]
acids in the Suzuki reaction and other coupling reactions. These
salts can be readily prepared through a variety of one-pot synthetic
[
15,16]
routes from readily available starting materials.
pling, which involved 5 mol% PdCl and 1 equiv. of potassium
2
Apart from the classical and/or modified coupling reactions
acetate in dimethylsulfoxide (DMSO) at 60°C, were initially exam-
ined (Table 1, entry 1). The desired 4-methylbiphenyl product (3a)
was formed in less than 5% assay yield. We were concerned that
catalytic activity was an issue, so we used ligands that proved to
with aryl halides as the electrophiles via the cleavage of C– X
[17–24]
bonds (Scheme 1),
organotrifluoroborate reagents can also
couple with arylsulfonates via the cleavage of C– O bonds
[
25–29]
(
Scheme 2),
including the more challenging unactivated
[30]
arylsulfamates. In addition, organotrifluoroborate reagents also
have been applied to couplings with aryl diazonium salts via the
cleavage of C– N bonds using suitable catalytic reaction
*
Correspondence to: Zhen Wei, College of Science, Hebei North University,
Zhangjiakou 075000, Hebei, China. E-mail: hnu_weizhen@126.com
[
31–35]
systems.
In recent years, decarboxylative reactions have
a College of Science, Hebei North University, Zhangjiakou 075000, Hebei, China
attracted a great deal of attention in organic synthesis for the con-
struction of carbon–carbon bonds, as carboxylic acids are com-
mon, inexpensive and readily available in great structural
diversity. Liu and co-workers reported a novel transition-metal-
catalyzed decarboxylative approach with organotrifluoroborates
b College of Basic Medicine, Hebei North University, Zhangjiakou 075000, Hebei,
China
c Physical Educational Research Group, First High School of Zhangjiakou, Hebei,
075000, China
Appl. Organometal. Chem. (2016)
Copyright © 2016 John Wiley & Sons, Ltd.

Wei Z., Xue D., Zhang H. and Guan J.
was performed with 1,4-bis (diphenylphosphino) butane (dppb),
the yield of 3a improved to 72% and the yield of 3a increased
to 84% when 1,2-bis(diphenylphosphino) ethane (dppe) was
utilized (Table 1, entries
diphenylphosphino) propane (dppp) as the ligand with PdCl
the catalyst, a 92% yield of the desired product was obtained
Table 1, entry 8). However, the use of other bisphosphine ligands,
such as 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) (rac-BINAP),
6
and 7). By using 1,3-bis(-
2
as
(
1
4
,1′-bis(diphenylphosphino) ferrocene (dppf) and 9,9-dimethyl-
,5-bis(diphenylphosphino) xanthene (xantphos), was relatively
ineffective in the coupling of 1a and 2a (Table 1, entries 9–11).
The addition of trialkylphosphines was generally inefficient for
the transformation, and the desired products were isolated in
the range of 27–44% (Table 1, entries 12–14).
Scheme 1. Cross-coupling of organotrifluoroborates via different types of
bond cleavage.
Our subsequent investigation focused on the effect of transition
metal catalysts, bases and solvents on the model reaction. The re-
sults are summarized in Table 2. Several Pd(0) salts were screened
in the presence of dppp as a ligand in DMSO, while all did not ex-
hibit catalytic activities (Table 2, entries 1 and 2). Reactions cata-
lyzed by other Pd salts, such as [Pd(C H )Cl] , Pd(TFA) and Pd
3
5
2
2
(
OAc) , either did not proceed or gave poor yields (Table 1, entries
2
3
–5). The use of Pd(CH CN) Cl and Pd(PhCN) Cl showed relatively
3 2 2 2 2
Table 2. Influence of catalysts, bases and solvents in cross-coupling of
a
aryl trifluoroborate with arylsulfonyl chloride
Scheme
2. Construction
of
heteroaryl–aryl/heteroaryl–heteroaryl
structures via desulfonative Pd-catalyzed coupling of aryl trifluoroborates
with arylsulfonyl chlorides.
Entry
Catalyst
Base
Solvent
DMSO
Yield (%)
Table 1. Influence of ligands in cross-coupling of aryl trifluoroborate
1
Pd
Pd(Ph
[Pd(C
Pd(TFA)
Pd(OAc)
Pd(CH CN)
Pd(PhCN) Cl
PdCl
PdCl
2
(dba)
P)
)Cl]
3
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
—
—
—
53
60
82
87
92
66
71
75
77
80
88
84
—
—
83
87
82
89
85
88
81
a
with arylsulfonyl chloride
2
3
4
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
Mesitylene
t-AmOH
DCE
3
3
H
5
2
4
2
5
2
6
3
2 2
Cl
7
2 2
8
2
Entry
Ligand
Yield (%)
Entry
Ligand
dppp
Yield (%)
9
2
NaHCO
Na CO
3
1
2
3
4
5
6
7
—
—
23
49
57
62
72
84
8
9
92
55
61
64
37
27
44
10
11
12
13
14
15
16
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
2
3
PPh
P(p-tol)
P(m-tol)
P(o-tol)
3
rac-BINAP
dppf
K2CO3
3
10
11
12
13
14
Cs CO
2
3
3
xantphos
‵t-BuOK
K3PO4
NaOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
3
PCy
P(i-Pr)
P(t-Bu)
3
dppb
dppe
3
3
17
PdCl
PdCl
PdCl
PdCl
PdCl2
PdCl
PdCl
PdCl
2
a
18
2
Reaction conditions: phenyl trifluoroborate (0.5 mmol), 4-
(5 mol%), ligand (10
19
2
3
CH CN
methylphenylsulfonyl chloride (0.6 mmol), PdCl
2
mol%), KOAc (0.5 mmol), DMSO (1.0 ml) at 60°C for 6 h unless
otherwise indicated.
20
21
2
NMP
DME
22
23
24
2
CPME
THF
2
2
Diglyme
be effective in the cross-coupling reactions. Triphenylphosphine
was first tested and a slightly higher yield was obtained (Table 1
a
Reaction conditions: phenyl trifluoroborate (0.5 mmol), 4-
methylphenylsulfonyl chloride (0.6 mmol), catalyst (5 mol%), dppp (10
mol%), base (0.5 mmol), solvent (1.0 ml) at 60°C for 6 h unless
otherwise indicated.
,
entry 2). Further screening of monophosphine ligands, such as
P(p-tol)3, P(m-tol) and P(o-tol) , indicated that P(o-tol) was most
effective in affording 3a (Table 1, entries 3–5). When the reaction
3
3
3
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. (2016)

Desulfonative coupling of aryl trifluoroborates with sulfonyl chlorides
higher efficiency, and 82–87% yields of biaryls were obtained
corresponding cross-coupling products in 93 and 90% yield (Table 3
, entries 1 and 2). And also, halogenated phenyl trifluoroborates
2
(Table 2, entries 6 and 7). We observed that PdCl showed higher
activity than other palladium catalysts, providing 4-methylbiphenyl
in 92% yield (Table 2, entry 8) in the presence of KOAc in DMSO. A
3 3
such as p-FPhBF K and p-ClPhBF K could cross-couple smoothly
with phenylsulfonyl chloride in good yields (Table 3, entries 4 and
5). However, phenyl trifluoroborates with electron-poor substitu-
number of bases such as NaHCO
to give the coupling product in good yield (Table 2, entries 9–12).
Among bases explored, t-BuOK, K PO and NaOAc afforded the de-
sired arylation products with 80, 88 and 84% yields (Table 2, entries
3–15). In the next stage, we examined the effect of the solvent on
3 2 3 2 3 2 3
, Na CO , Cs CO and K CO failed
2 3
ents such as NO and OCF generated the desired product in a
3
4
slightly lower yield (Table 3, entries 6 and 7). In addition, ortho-
and meta-substituted aryl trifluoroborates could also be well toler-
ated, generating the desired coupling products in moderate to
good yields (Table 3, entries 8–11). Notably, the bromo and iodo
groups, which are extremely reactive in Suzuki reaction, were well
tolerated by this Pd-catalyzed cross-coupling method (Table 3, en-
tries 12 and 13). It should be noted that reactions of heterocyclic
trifluoroborates also proceeded smoothly (Table 3, entries 14–16).
To our delight, relatively challenging amino functional groups were
still tolerated with this coupling condition, even with free-amino
substituent (Table 3, entries 17 and 18). Amide-substituted phenyl
trifluoroborate was also a good coupling partner with wonderful
functional tolerance (Table 3, entry 19). Otherwise, (E)-cinnamenyl
trifluoroborate was easily coupled with phenylsulfonyl chloride to
generate trans-1,2-diphenylethene in a yield of 86%, expanding
the application scope of this reaction (Table 3, entry 20).
1
the reaction (Table 2, entries 16–24). However, the reaction did not
proceed in mesitylene or t-AmOH (tertiary amyl alcohol) (Table 2,
entries 16 and 17). Among the solvents (CH CN, DCE, NMP and
3
DME) tested, DME gave the best result (Table 2, entries 18–21).
Three additional ethereal solvents (cyclopentyl methyl ether
(CPME), diglyme and THF) were surveyed with DME giving a better
yield (Table 2, entries 22–24). Further optimization did not lead to
increased yields, such as increasing the temperature of the reaction
and doubling the reaction time. Thus, the optimized conditions
were 5 mol% PdCl , dppp as the ligand, 1 equiv. of KOAc in DMSO
2
at 60°C for 6 h.
Furthermore, considerable efforts have been made to test the
substrate generality of this reaction under the optimized reaction
conditions. First, different aryl trifluoroborates were tested to cou-
ple with phenylsulfonyl chloride to afford the corresponding prod-
ucts (Table 3). Notably, this reaction has a good compatibility for
different groups on aryl rings. Phenyl trifluoroborates with p-MeO
and p-Me substituents could be well tolerated, affording the
Next, we applied this catalytic system to various arylsulfonyl chlo-
rides to demonstrate the efficiency and scope of the present
method (Table 4). Phenyl trifluoroborate was reacted with
phenylsulfonyl chloride to produce biphenyl in 95% yield (Table 4
, entry 1). The presence of an electron-donating group such as
methoxy group on the phenyl ring did not lower the product yield
Table 3. Cross-coupling of various aryl trifluoroborates with
a
phenylsulfonyl chloride
Table 4. Cross-coupling of phenyl trifluoroborate with various
arylsulfonyl chlorides
a
Entry
R
Yield (%)
Entry
R
Yield (%)
1
2
3
4
5
6
7
8
9
4-CH
4-CH
3
OC
6
H
4
93
90
94
86
88
82
77
89
87
85
84
89
83
84
88
79
87
71
80
86
3 6
C H
4
1
C
6
H
5
95
91
87
92
84
88
86
88
83
92
87
80
86
79
75
72
82
84
85
C H
6 5
2
4-CH
4-FC
4-ClC
4-CNC
4-NO
4-CF
3-CH
3-CF
4-CH
3-CH
2-CH
3 6 4
OC H
4-FC
4-ClC
4-NO
4-CF
3-CH
3-CH
3-NO
2-CH
4-BrC
4-IC
6
H
4
3
6 4
H
6 4
H
4
6 4
H
2 6
C H
4
5
6 4
H
3
OC
OC
6
H
4
6
2 6 4
C H
3
6
H
4
7
3 6 4
C H
3
6
C H
4
8
3 6 4
OC H
10
11
12
13
14
15
16
17
18
19
20
2 6
C H
4
9
3 6 4
C H
3
6
C H
4
10
11
12
13
14
15
16
17
18
19
3 6 4
C H
6 4
H
3 6 4
C H
6
H
4
3 6 4
C H
2-Thienyl
2-Furyl
2-Naphthyl
1-Naphthyl
3-Pyridyl
4-HOC
4-CHOC
4-AcC
4-CH OOCC
2-Pyridyl
6 4
H
4-Me
4-NH
4-NH
trans-Styryl
2
NC
6
H
4
6 4
H
2 6
C H
4
6 4
H
2
COC
6
H
4
3
6 4
H
a
a
Reaction conditions: aryl trifluoroborate (0.5 mmol), phenylsulfonyl
(5 mol%), dppp (10 mol%), KOAc (0.5
mmol), DMSO (1.0 ml) at 60°C for 6 h unless otherwise indicated.
Reaction conditions: phenyl trifluoroborate (0.5 mmol), arylsulfonyl
(5 mol%), dppp (10 mol%), KOAc (0.5
chloride (0.6 mmol), PdCl
2
chloride (0.6 mmol), PdCl
mmol), DMSO (1.0 ml) at 60°C for 6 h unless otherwise indicated.
2
Appl. Organometal. Chem. (2016)
Copyright © 2016 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/aoc

Wei Z., Xue D., Zhang H. and Guan J.
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