Pd-catalyzed desulfitative Hiyama coupling with sulfonyl chlorides

Article abstract of DOI:10.1002/aoc.3139

Palladium-catalyzed desulfitative Hiyama cross-coupling reactions of various arylsulfonyl chlorides with aryltriethoxysilane have been achieved in good yields. The reported cross-coupling reactions are tolerant to the common functional groups regardless o

Full text of DOI:10.1002/aoc.3139

Full Paper
Received: 25 December 2013
Revised: 17 February 2014
Accepted: 17 February 2014
Published online in Wiley Online Library: 1 April 2014
(wileyonlinelibrary.com) DOI 10.1002/aoc.3139
Pd-catalyzed desulfitative Hiyama coupling
with sulfonyl chlorides
Wei Zhanga, Fang Liub, Ke Lic and Baoli Zhaod*
Palladium-catalyzed desulfitative Hiyama cross-coupling reactions of various arylsulfonyl chlorides with aryltriethoxysilane
have been achieved in good yields. The reported cross-coupling reactions are tolerant to the common functional groups
regardless of electron-withdrawing or electron-donating, making these transformations attractive alternatives to the
traditional cross-coupling approaches. Copyright © 2014 John Wiley & Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web-site.
Keywords: Pd-catalyzed; desulfitative coupling; Hiyama cross-coupling; arylsulfonyl chloride
NMP were also 47–59% (Table 1, entries 2–4). Ether solvents such
as 1,4-dioxane and THF have been tested, and no better results
Introduction
Arylsulfonyl chlorides are inexpensive and readily available
compounds. They have been used for many years in industry
for the manufacture of drugs, pesticides, dyes, polymers, etc.[1,2]
However, the application of arylsulfonyl chlorides in transition
metal-catalyzed C―C bond-forming reactions was obscured until
1988. The first job using arylsulfonyl chlorides as reagents in
Pd-catalyzed Heck-type cross-coupling reactions was reported
by Kasahara and Miura.[3–6] Development came to a standstill
for more than 10 years until Vogel’s series of achievement were
published from 2003.[7]
Arylsulfonyl chlorides have been demonstrated as a class of elec-
trophilic reagents in Pd-catalyzed desulfitative C―C cross-coupling
reactions since then. Many types of coupling reaction, such as
Negishi,[8] Stille,[9–11] Suzuki,[12] Heck,[13] Sonogashira,[14–16]
homocoupling[17,18] and carbonylation[19] have been well devel-
oped. However, it has not been extended to Pd-catalyzed C―C
bond formation with organosilanes (Hiyama cross-coupling; Fig. 1).
Hiyama reaction has drawn increasing attention as one of the
useful synthetic methods for the construction of asymmetrical
biaryls.[20–23] Organosilanes are very stable, low toxicity[24,25] and
the leaving silicon group can be converted to harmless SiO2 by
incineration,[26,27] which has made this method attractive from an
environmentally friendly point of view. We report here a new
application to arylsulfonyl chlorides in Hiyama-type cross-coupling
under mild conditions without ligands.[28]
were obtained (Table 1, entries 5 and 6). Acetonitrile was coped
with the cross-coupling; however, toluene inhibited its activity
(Table 1, entries 7 and 8). Subsequently, we further considered
the application of component solvent. We chose the DMF (which
showed the best in solvent selection) to mix with the other
solvent. To our delight, the mixture displayed an obvious effect
to the cross-coupling reaction (69–75%) (Table 1, entries 9–11)
and solvent consisting of DMF and CH3CN (volume ratio 1:1)
was shown to be best (Table 1, entry 12). Finally, we adjusted
the constitution of DMF and CH3CN in the range of 9:1 to 1:9
(Table 1, entries 13–20). A volume ratio of 1:4 (DMF vs. CH3CN)
was chosen for the following optimization (Table 1, entry 19).
As shown in Table 2, the effects of catalysts and additives were
investigated. We tested various Pd catalysts for this desulfinative
coupling reaction by using DMF/CH3CN (1:4) as the solvent and
TBAF.3H2O as the additive. Among palladium catalysts explored,
Pd(dppf)Cl2, PdCl2(PPh3)2 and PdCl2(CH3CN)2 afforded the desired
biphenyl with 45%, 39% and 49% yields (Table 2, entries 1–3). Al-
though Pd(OAc)2 and PdCl2 afforded the same or a higher yield of
the desired product (Table 2, entries 4 and 5), the Pd(0) catalysts
showed better catalytic activities. The screening of non-valent pal-
ladium catalysts, such as Pd(PPh3)4, Pd(dba)2 and Pd2(dba)3, pro-
vided 4-methyl-1,1′-biphenyl in 87%, 83% and 91% yield,
*
Correspondence to: Baoli Zhao, Institute of Applied Chemistry and Department of
Chemistry, Shaoxing University, Shaoxing, Zhejiang Province 312000, People’s
Republic of China. E-mail: babygarfield@126.com
Results and Discussion
a Department of Chemistry and Chemical Engineering, Xinxiang University,
Xinxiang, Henan Province 453003, People’s Republic of China
We initiated our investigation on the model reaction of
p-methylphenylsulfonyl chloride with phenyltrimethoxysilane to
optimize the cross-coupling conditions. To our delight, the
desulfitative cross-coupling took place in the presence of Pd2
(dba)3 (3 mol%) and TBAF.3H2O (n-tetrabutylammonium fluoride)
(1 equiv.) in DMSO under N2 with a yield of 52% (Table 1, entry 1).
We then investigated the influence of solvents on reaction activ-
ity. The optimization results are shown in Table 1. The yields
obtained in other polar aprotic solvents like DMF, DMA and
b Life Science Research Center, Hebei North University, Zhangjiakou, Hebei
Province 075000, People’s Republic of China
c
Jiaozuo City Environmental Protection Bureau, Jiaozuo, Henan Province
453003, People’s Republic of China
d Institute of Applied Chemistry and Department of Chemistry, Shaoxing University,
Shaoxing, Zhejiang Province 312000, People’s Republic of China
Appl. Organometal. Chem. 2014, 28, 379–381
Copyright © 2014 John Wiley & Sons, Ltd.

W. Zhang et al.
Table 2. Screening of various catalysts and additivesa
Entry
Catalyst
Additive
TBAF.3H2O
Yield (%)b
1
Pd(dppf)Cl2
PdCl2(PPh3)2
Pd(CH3CN)2Cl2
Pd(OAc)2
PdCl2
45
39
49
58
63
87
83
91
—
19
13
—
—
—
Figure 1. Arylsulfonyl chlorides in Pd-catalyzed coupling.
2
TBAF.3H2O
TBAF.3H2O
TBAF.3H2O
TBAF.3H2O
TBAF.3H2O
TBAF.3H2O
TBAF.3H2O
TBAF.3H2O
TBAF(1 M in THF)
TBAF (75% in water)
NaF
3
respectively (Table 2, entries 6–8). No product was formed in the
presence of heterogeneous Pd/C catalyst(Table 2, entry 9). Thus
Pd2(dba)3 was selected for further optimization. Subsequently, we
started to investigate a variety of additives (fluorochemical) to favor
the removal of silicon groups. Intriguingly, when TBAF.3H2O was
used as the additive, it gave a 91% yield of biphenyls, whereas
the use of TBAF (1M in THF) and TBAF (75% water) gave less than
20% of the product (Table 2, entries 10 and 11). Furthermore, the
reaction did not proceed well when carried out with other addi-
tives, such as NaF, KF and CsF (Table 2, entries 12–14).
4
5
6
Pd(PPh3)4
Pd(dba)2
Pd2(dba)3
Pd/C
7
8
9
10
11
12
13
14
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
KF
Hence the scope of the direct desulfinative coupling with
arylsulfonyl chloride was explored by using 5 mol% Pd2(dba)3 as
the catalyst and TBAF as the additive in DMF/CH3CN at 100°C un-
der nitrogen. As summarized in Table 3, the palladium-catalyzed
desulfinative coupling of phenyltriethoxysilane was successfully
extended to various arylsulfonyl chloride substrates with differ-
ent substituents at the para, meta or ortho position of the aro-
matic ring, and the desired biaryls were obtained in moderate
to good yields. The reaction could tolerate a range of functional
groups at the para position with coupling occurring in the pres-
ence of methoxy group, acetyl group and nitro group (Table 3,
CsF
aReaction conditions: p-methylphenylsulfonyl chloride (0.5 mmol),
phenyltriethoxysilane (0.5 mmol), catalyst (3 mol%), additive
(0.5 mmol), DMF/CH3CN (1:4) (1.0 ml) at 100°C for 3 h under N2.
bIsolated cross-coupling yield.
entries 1–5). The ability to incorporate chloro and bromo substit-
uents makes this reaction particularly attractive for transition
metal-catalyzed coupling reactions (Table 3, entries 6 and 7).
Table 1. Solvent selection of Pd-catalyzed cross-coupling
Entry
Solvent
DMSO
Yield (%)b
Entry
Solvent
Yield (%)b
1
2
3
4
5
6
7
8
9
10
52
59
56
40
46
48
50
—
69
75
11
12
13
14
15
16
17
18
19
20
DMF/1,4-dioxane (1:1)
DMF/ CH3CN (1:1)
DMF/ CH3CN (9:1)
DMF/ CH3CN (4:1)
DMF/ CH3CN (3:1)
DMF/ CH3CN (2:1)
DMF/ CH3CN (1:2)
DMF/ CH3CN (1:3)
DMF/ CH3CN (1:4)
DMF/ CH3CN (1:9)
73
79
74
79
76
81
85
81
91
87
DMF
DMA
NMP
1,4-Dioxane
THF
CH3CN
Toluene
DMF/DMSO (1:1)
DMF/THF (1:1)
aReaction conditions: p-methylphenylsulfonyl chloride (0.5mmol), phenyltriethoxysilane (0.5mmol), Pd2(dba)3 (3mol%), TBAF.3H2O (0.5mmol),
solvent (1.0 ml) at 100°C for 3 h unless otherwise indicated.
bIsolated cross-coupling yield; the v/v ratio of solvents shown in parentheses.
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Copyright © 2014 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2014, 28, 379–381

Pd-catalyzed desulfitative Hiyama coupling with sulfonyl chlorides
Table 3. Pd-catalyzed desulfitative Hiyama coupling with sulfonyl
chloridesa
Entry
R1
4-OMe
R2
Yield (%)b
1
H
90
91
86
78
81
89
83
80
74
90
76
92
87
83
86
79
82
88
77
83
71
Figure 2. Possible mechanism.
2
4-CH3
H
3
4-t-Bu
H
4
4-COMe
H
Conclusion
5
4-NO2
H
H
6
4-Cl
We disclose here the first cross-coupling of arylsulfonyl chloride
with aryltrimethoxysilane to afford biaryl products. The Pd(0)-
catalyzed Hiyama-type reaction proceeded smoothly in DMF/
CH3CN under N2. This transformation was efficient via desulfitative
course with the assistance of TBAF.3H2O.
7
4-Br
H
8
3-OMe
H
9
2-OMe
H
10
11
12
13
14
15
16
17
18
19
20
21
2-Naphthyl
H
1-Naphthyl
H
H
H
H
H
H
H
H
H
H
H
4-OMe
4-CH3
4-t-Bu
4-Cl
References
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1-Naphthyl
aReaction conditions: arylsulfonyl chloride (0.5 mmol), aryltriethoxysilane
(0.5 mmol), Pd2(dba)3 (3 mol%), TBAF.3H2O (0.5mmol), DMF/CH3CN
(1:4) (1.0 ml) at 100°C for 3 h under N2 unless otherwise indicated.
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However, the site-diverse groups on the phenyl ring of arylsilane
would slightly decrease the reaction efficiency (Table 3, entries
8 and 9). After a broad scope of arylsulfonyl chloride was
established, we were particularly interested in extending the
arylation to arylsilane derivatives. 4- Methoxy, 4-chloro, 4-bromo,
4-nitro and 4-tert-butyl could be coupled with good effi-
ciency (Table 3, entries 12–17). Importantly, naphthalene
groups were also applicable to these reaction conditions in
moderate to good yield, no matter whether naphthalene-
sulfonyl chloride or trimethoxy(naphthalen-2-yl)silane (Table 3,
entries 10, 11, 20, 21).
A plausible mechanism is outlined in Fig. 2. Step (i) involves
the oxidative addition of arylsulfonyl chloride to the Pd(0)
forms the Pd(II) intermediate A. In step (ii), the intermediate
A produces intermediate B with concomitant loss of SO2 in
the presence of palladium catalysts at a higher temperature,
the exchange of arylsilane with intermediate B in step (iii) to
afford intermediate C by the assistance of TBAF and, in step Supporting Information
(iv), the reductive elimination from the Pd(II) complex affords
the biaryl and regenerates Pd(0).
Additional supporting information may be found in the online
version of this article at the publisher's web-site.
Appl. Organometal. Chem. 2014, 28, 379–381
Copyright © 2014 John Wiley & Sons, Ltd.
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