Palladium-catalyzed Hiyama-type cross-coupling reactions of arenesulfinates with organosilanes

Article abstract of DOI:10.1021/jo302791q

Palladium-catalyzed Hiyama-type cross-coupling reactions of various arenesulfinates with organosilanes were achieved in good to excellent yields under aerobic conditions at 70 °C. Fluoride is essential, and tetrabutylammonium fluoride (TBAF) was shown to

Full text of DOI:10.1021/jo302791q

Note
pubs.acs.org/joc
Palladium-Catalyzed Hiyama-Type Cross-Coupling Reactions of
Arenesulfinates with Organosilanes
Kai Cheng,†,§ Sai Hu,‡ Baoli Zhao,† Xian-Man Zhang,† and Chenze Qi*,†
†Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, Shaoxing University, Shaoxing 312000, People’s
Republic of China
‡College of Materials Science and Chemical Engineering, Ningbo University, Ningbo 310014, People’s Republic of China
§Zhejiang Huangma Chemical Industry Group Co. Ltd., Shangyu, Zhejiang Province 312363, People’s Republic of China
S
* Supporting Information
ABSTRACT: Palladium-catalyzed Hiyama-type cross-coupling
reactions of various arenesulfinates with organosilanes were
achieved in good to excellent yields under aerobic conditions at
70 °C. Fluoride is essential, and tetrabutylammonium fluoride (TBAF) was shown to be the most efficient additive for these
cross-coupling reactions. These cross-coupling reactions of the arenesulfinates provide high yields and show wide functional
group tolerance, making them attractive alternative transformations to traditional cross-coupling approaches for carbon−carbon
bond construction.
Scheme 1
ransition-metal-catalyzed cross-coupling reactions of
Torganometallic reagents with organic halides have become
routine tools for the construction of C−C bonds in synthetic
organic chemistry.1 Organoboron,2 organozinc,3 and organotin4
reagents are among the most common substrates for the Pd-
catalyzed cross-coupling reactions, but these coupling partners
have inherent drawbacks such as high cost, high toxicity, low
stability, and poor biocompatibility. In contrast, organosilicon
reagents have emerged as competitive alternatives for the
nucleophilic partners for cross-coupling reactions with various
organic halides or pseudohalides, primarily due to their low
toxicity, high chemical stability, and broad availability.5
Tremendous progress has been made for the Hiyama cross-
coupling reactions in the organic synthesis of natural products
and biologically active compounds.6 Thus, it will be valuable to
develop new reagents for the Hiyama cross-coupling reactions,
extending the scope and generality of their synthetic
applications.
decarboxylative coupling reactions, arenesulfinates have been
shown to be more reactive substrates for the synthesis of
various aromatic compounds.12 Arylsulfonyl chlorides have
typically been used as aryl sources, however, they are not stable
and moisture sensitive. Sodium arylsulfinates are stable and easy
to handle, which shows great potential as aryl sources. Herein,
we report our results of the Pd-catalyzed Hiyama-type cross-
coupling reactions of various arenesulfinates with different
organosilicon reagents in the absence of bases and ligands
under mild reaction conditions (Scheme 1, D). Scheme 1
summarizes the key bond cleavages of the electrophilic reagents
for several Hiyama-type cross-coupling reactions.
Traditionally, the Hiyama cross-coupling reactions involve
aryl halides as the electrophilic reagents by the cleavage of the
corresponding carbon−halogen bonds (Scheme 1, A).7 While
the carbon−oxygen bond cleavage of the electrophilic reagents
such as aryl tosylates/mesylates has been reported (Scheme 1,
B),8 fairly little work has been reported concerning the carbon−
nitrogen bond cleavage of the electrophilic reagents for the
Hiyama cross-coupling reactions in the literature. Recently, we
reported a practical carbon−nitrogen bond cleavage procedure
for the Hiyama cross-coupling reactions using arenediazonium
salts as the electrophilic reacgents (Scheme 1, C).9 To the best
of our knowledge, no carbon−sulfur bond cleavage of the
corresponding electrophilic reagents has yet been reported in
the literature for the Hiyama cross-coupling reactions even
though arenesulfinates were employed as electrophilic partners
for Heck cross-coupling reactions10 and for carbon−hydrogen
activation.11 As an alternative for aromatic carboxylic acids for
Our initial screening experiments started with the reaction of
phenyltriethoxysilane with sodium p-methylbenzenesulfinate in
the presence of n-tetrabutylammonium fluoride (TBAF,
dissolved in THF) and 5 mol % of Pd(OAc)
under
2
atmospheric air for 3 h at 70 °C, resulting in the formation of
Received: January 14, 2013
© XXXX American Chemical Society
A
dx.doi.org/10.1021/jo302791q | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
the corresponding cross-coupling product in good yield (75%)
(entry 1, Table 1). This cross-coupling was then employed as a
addition of TBAF (1 M in THF) and TBAF·3H2O has no
major effect on the cross-coupling yield, suggesting that the
corresponding transformation can tolerate a stoichiometric
amount of water. Nevertheless, only about 64% of the cross-
coupling yield was obtained using TBAF (75% aqueous) in
DMSO solution (entry 3, Table 2). Examination of entries 4
6 of Table 2 shows that the cross-coupling yield gradually
increases from 54% to 81% to 90% as the additive changes from
NaF to KF to CsF, respectively, presumably due to solubility of
the fluoride.13 The yields decreasing when THF was used as
solvent (entries 3−6, Table 2, in parentheses). Recently, we
Table 1. Catalyst Optimization for the Hiyama-Type Cross-
a
Coupling
b
entry
catalyst
Pd(OAc)2
yield (%)
1
75
55
63
54
76
74
60
57
91
94
∼0
∼0
2
PdCl2(PPh3)2
Pd(PCy3)2Cl2
Pd(dppf)Cl2
Pd(PhCN)2Cl2
Pd(CH3CN)2Cl2
Pd(PPh3)4
−
have shown that the BF4 anion may be involved with the
3
acceleration of the Hiyama-type cross-coupling reactions of
arenediazonium salts,9 but clearly the BF4− anion has no effects
on the Hiyama-type cross-coupling of p-methylbenzenesulfinate
with phenyltriethoxysilane in methanol (entry 7, Table 2).
Selectfluor was also tested, and no desired product was
detected (entry 8, Table 2).
The optimized PdCl2-catalyzed protocol was applicable to
the cross-coupling reactions of a wide variety of arenesulfinates
with different organosilanes as evidenced from Table 3.
4
5
6
7
8
Pd2(dba)3
9
PdI2
10
11
12
PdCl2
RhCl(PPh3)3
[RuCl2(p-cymene)]2
a
Reaction conditions: phenyltriethoxysilane (0.6 mmol), sodium p-
Table 3. PdCl2-Catalyzed Hiyama-Type Cross-Coupling of
methylbenzenesulfinate (0.5 mmol), catalyst (5.0 mol %), TBAF (1 M
a
b
Arenesulfinates with Organosilanes
in THF, 1 mL), 3 h. Isolated cross-coupling yields.
model reaction to further optimize the palladium catalytic
system, and the related results are also summarized in Table 1
for comparison. Examination of entries 2−8 of Table 1 shows
that the cross-coupling products were obtained in comparable
yields when several palladium catalysts were used. Most
interestingly, much higher cross-coupling yields were obtained
when PdI2 and PdCl2 compounds were used as the catalyst
(entries 9 and 10, Table 1), which are structurally less complex
and less expansive than the other catalyst. Negligible cross-
coupling products were formed when the ruthenium and
rhodium compounds were used as the catalysts for the cross-
coupling reactions (entries 11 and 12, Table 1).
b
entry
arenesulfinates
organosilanes
yield (%)
1
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeO-C6H4SO2Na
4-ClC6H4SO2Na
4-BrC6H4SO2Na
4-FC6H4SO2Na
C6H5Si(OEt)3
C6H5Si(OMe)3
(C6H5)2Si(OMe)2
4-MeC6H4Si(OMe)3
3-FC6H4Si(OMe)3
4-CF3C6H4Si(OMe)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
C6H5Si(OEt)3
94
91
90
88
86
87
92
84
86
79
73
89
77
79
84
81
80
73
82
85
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
We then examined effects of solvents and additives on the
PdCl2-catalyzed cross-coupling of phenyltriethoxysilane with p-
methylbenzenesulfinate, and the key results are summarized in
Table 2. Examination of entries 1 and 2 of Table 2 shows that
4-NO2C6H4SO2Na
3-MeC6H4SO2Na
3-NO2C6H4SO2Na
3-FC6H4SO2Na
3,5-MeC6H4SO2Na
2-MeC6H4SO2Na
2-ClC6H4SO2Na
2,6-MeC6H4SO2Na
1-naphthyl-SO2Na
2-naphthyl-SO2Na
Table 2. Effects of the Additives on the Hiyama-Type Cross-
a
Coupling
a
Reaction conditions: silanes (0.6 mmol), arenesulfinate (0.5 mmol),
b
b
entry
additives
solvents
THF
yield (%)
PdCl2 (5 mol %), TBAF (1 M in THF, 1 mL), 3 h. Isolated cross-
coupling yields.
1
2
3
4
5
6
7
8
TBAF (1 M in THF)
94
TBAF·3H2O
TBAF (75% water)
NaF
THF
88
DMSO (THF)
DMSO (THF)
DMSO (THF)
DMSO (THF)
CH3OH
64 (47)
54 (32)
81 (45)
90 (49)
Examination of entries 16 of Table 3 shows that essentially
comparable yields (90
4%) were obtained for the cross-
KF
coupling reactions of p-methylbenzenesulfinate regardless of
the silane chemical structures (phenyltriethoxysilanes, phenyl-
trimethoxysilanes or dimethoxydiphenylsilane) and the aro-
matic ring substituents. Most intriguingly, the Hiyama-type
cross-coupling reactions (entries 7−20, Table 3) also afforded
good reaction yields regardless of the polarity of the aromatic
ring substituents. Moreover, the Hiyama-type cross-coupling
reactions were tolerant to steric hindrance of the ortho
CsF
NaBF4
Selectfluor
CCl4
a
Reaction conditions: phenyltriethoxysilane (0.6 mmol), sodium p-
methylbenzenesulfinate (0.5 mmol), PdCl2 (5 mol %), additive (0.5
mmol), solvent (1.0 mL), 3 h. Isolated cross-coupling yields. The
yields of entries using THF as solvent were shown in parentheses.
b
B
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Note
The cross-coupling products were confirmed by melting points and
spectroscopic (1H NMR and HRMS-EI) analysis, which were all
consistent with the literature results.
substituent(s) (entries 16−19, Table 3) as well as halogen
substituents (entries 810 and 14, Table 3). The excellent
tolerance for a wide range of functional groups and the steric
hindrance reveals that these straightforward transformations
can be used as an effective method under very mild reaction
conditions for the construction of C(sp2)−C(sp2) bonds in the
organic synthesis.
A plausible mechanism for the Hiyama-type cross-coupling
reaction of arenesulfinates with aryl siloxanes is shown in Figure
1. The PdCl2 catalyst may first react with arenesulfinate to form
4-Methyl-1,1′-biphenyl (T3-1, CAS no. 644-08-6): white solid;
mp 46−47 °C (lit.1b mp 47−48 °C); H NMR (400 MHz, CDCl3,
1
TMS) δ 7.55 (t, J = 6.8 Hz, 2 H), 7.38−7.48 (m, 4 H), 7.32 (t, J = 7.2
Hz, 1 H), 7.21 (d, J = 7.6 Hz, 2 H), 2.33 (s, 3 H). HRMS (EI) calcd
for C13H12 (M+) 168.0939, found 168.0938.
4,4′-Dimethyl-1,1′-biphenyl (T3-4, CAS no. 613-33-2): white
solid; mp 120−121 °C (lit.1c mp 119−120 °C); 1H NMR (400 MHz,
CDCl3, TMS) δ 7.47 (d, J = 8.0 Hz, 4 H), 7.45 (d, J = 7.6 Hz, 4 H),
2.37 (s, 6 H); HRMS (EI) calcd for C14H14 (M+) 182.1096, found
182.1099.
3-Fluoro-4′-methyl-1,1′-biphenyl (T3−5, CAS no. 72093-42-
6): white solid; mp 39−40 °C (lit.1c mp 39−40 °C); H NMR (400
1
MHz, CDCl3, TMS) δ 7.44 (t, J = 8.0 Hz, 2 H), 7.28−7.35 (m, 2 H),
7.19−7.23 (m, 3 H), 7.02 (t, J = 8.0 Hz, 1 H), 2.35 (s, 3 H); HRMS
(EI) calcd for C13H11F (M+) 186.0841, found 186.0841.
4-Methyl-4′-(trifluoromethyl)-1,1′-biphenyl (T3-6, CAS no.
97067-18-0:). white solid; mp 122−124 °C (lit.1d mp 121 °C); H
1
NMR (400 MHz, CDCl3, TMS) δ 7.65−7.72 (m, 4 H), 7.46 (d, J =
7.2 Hz, 2 H), 7.21 (d, J = 7.6 Hz, 2 H), 2.37 (s, 3 H); HRMS (EI)
calcd for C14H11F3 (M+) 236.0813, found 236.0815.
4-Methoxy-1,1′-biphenyl (T3−7, CAS no. 613−37-6): white
solid; mp 88−90 °C (lit.1b mp 88−89 °C); H NMR (400 MHz,
1
CDCl3, TMS) δ 7.54 (t, J = 8.8 Hz, 4 H), 7.39 (t, J = 7.6 Hz, 2 H),
7.30 (t, J = 7.6 Hz, 1 H), 6.95 (d, J = 8.8 Hz, 2 H), 3.81 (s, 3 H);
HRMS (EI) Calcd for C13H12O (M+) 184.0888, found 184.0884.
4-Cholro-1,1′-biphenyl (T3−8, CAS no. 644-08-6): white solid;
Figure 1. Mechanism proposed.
mp 48−49 °C (lit.1b mp 47−48 °C); H NMR (400 MHz, CDCl3,
1
the ArS(O)OPdX reactive intermediate (Figure 1, A),
followed by expulsion of SO2 to produce the ArPdX reactive
intermediate, which is similar to the palladium intermediates
proposed in many other homo- and/or cross-coupling
reactions.14 The ArPdAr′ (Figure 1, B) reactive intermediate
will be formed with the assistance of TBAF from the
transmetalation of the ArPdX reactive intermediate with
organosilane. Indeed, the formation of Si(OEt)3Cl for reactions
of aryltriethoxysilanes was detected by the GC/MS analysis.
Reductive elimination of the biaryl coupling products is
accompanied by formation of the reduced Pd0 species, which
can be oxidized by atmospheric oxygen to furnish the catalytic
cycle for the cross-coupling of arenesulfinates with organo-
silanes. The byproduct sulfur dioxide (SO2) could be further
neutralized using ammonia aqueous solution to produce
ammonium sulfinate [(NH4)2SO3], a common fertilizer with
no environmental pollution for industrial process.15
TMS) δ 7.56 (t, J = 6.8 Hz, 2 H), 7.40−7.48 (m, 4 H), 7.32 (t, J = 7.2
Hz, 1 H), 7.22 (d, J = 7.6 Hz, 2 H); HRMS (EI) calcd for C12H9Cl
(M+) 188.0393, found 188.0396.
4-Bromo-1,1′-biphenyl (T3−9, CAS no. 92-66-0): white solid;
mp 90−92 °C (lit.1b mp 91−92 °C); H NMR (400 MHz, CDCl3,
1
TMS) δ 7.58 (d, J = 7.2 Hz, 1 H), 7.51−7.54 (m, 3 H), 7.39−7.43 (m,
3 H), 7.30−7.37 (m, 2 H); HRMS (EI) calcd for C12H9Br (M+)
231.9888, found 231.9887.
4-Fluoro-1,1′-biphenyl (T3−10, CAS no. 324-74-3): white
solid; mp 73−74 °C (lit.1e mp 73−74 °C); H NMR (400 MHz,
1
CDCl3, TMS) δ 7.52−7.56 (m, 4 H), 7.43 (t, J = 7.6 Hz, 2 H), 7.34 (t,
J = 7.2 Hz, 1 H), 7.12 (t, J = 8.4 Hz, 2 H); HRMS (EI) calcd for
C12H9F (M+) 172.0688, Found 172.0684.
4-Nitro-1,1′-biphenyl (T3−11, CAS no. 92-93-3): white solid;
mp 115−117 °C (lit.1b mp 115−116 °C); 1H NMR (400 MHz,
CDCl3, TMS) δ 8.28 (d, J = 8.4 Hz, 2 H), 7.72 (d, J = 9.2 Hz, 2 H),
7.62 (d, J = 6.8 Hz, 2 H), 7.42−7.51 (m, 3 H); HRMS (EI) calcd for
C12H9NO2 (M+) 199.0633, found 199.0634.
In summary, the PdCl2-catalyzed Hiyama-type cross-coupling
reactions of arenesulfinates with arylsiloxanes have been
achieved in excellent yields under very mild reaction conditions.
The widely available sodium arenesulfinates and broad
functional group tolerance enable this novel transformation to
be an attractive alternative to the Hiyama cross-coupling
reaction for carbon−carbon bond construction in organic
synthetic chemistry.
3-Methyl-1,1′-biphenyl (T3−12, CAS no 643-93-6): colorless
oil (lit.1e); 1H NMR (400 MHz, CDCl3, TMS) δ 7.58 (d, J = 7.2 Hz, 2
H), 7.38−7.44 (m, 4 H), 7.32 (t, J = 7.2 Hz, 2 H), 7.16 (d, J = 7.2 Hz,
1 H), 2.41 (s, 3 H); HRMS (EI) calcd for C13H12 (M+) 168.0939,
found 168.0937.
3-Nitro-1,1′-biphenyl ( 3−13, CAS no. 2113-58-8): white solid;
mp 59−60 °C (lit.1b mp 59−60 °C); H NMR (400 MHz, CDCl3,
1
TMS) δ 8.45 (s, 1 H), 8.19 (d, J = 8.4 Hz, 1 H), 7.91 (t, J = 8.0 Hz, 1
H), 7.58−7.63 (m, 3 H), 7.50 (t, J = 7.2 Hz, 2 H), 7.43 (t, J = 7.6 Hz, 1
H); HRMS (EI) calcd for C12H9NO2 (M+) 199.0633, found 199.0631.
3-Fluoro-1,1′-biphenyl (T3−14, CAS no. 2367-22-8): white
EXPERIMENTAL SECTION
■
solid; mp 26−27 °C (lit.1h mp 26−27 °C); H NMR (400 MHz,
1
General Procedure for the Cross-Coupling. A mixture of
arylsulfinate salt (0.50 mmol), PdCl2 (5 mol %), and aryltriethox-
ysilane (0.60 mmol) was stirred uncapped in the solvent of TBAF (1
M, in THF) (1.0 mL) at 70 °C for 3.0 h. After the mixture was cooled
to room temperature, water (5 mL) was added. The insoluble was
removed by filtration, and then the reaction mixture was extracted with
diethyl ether (Et2O) (2 mL) three times. The combined organic layer
was washed with water and saturated brine and then dried over
anhydrous sodium sulfate. Solvent was removed under reduced
pressure. The cross-coupling products were purified by silica gel
chromatography with a mixture of petroleum ether and ethyl acetate.
CDCl3, TMS) δ7.56 (d, J = 7.2 Hz, 2 H), 7.44 (t, J = 7.2 Hz, 2 H),
7.34−7.39 (m, 3 H), 7.28 (d, J = 10.0 Hz, 1 H), 7.00−7.05 (m, 1 H);
HRMS (EI) calcd for C12H9F (M+) 172.0688, found 172.0689.
2,6-Dimethyl-1,1′-biphenyl (T3−15, CAS no. 17057-88-4):
colorless oil (lit.1g); 1H NMR (400 MHz, CDCl3, TMS) δ7.60 (d, J =
7.2 Hz, 3 H), 7.44 (t, J = 7.6 Hz, 3 H), 7.34 (t, J = 7.2 Hz, 1 H), 6.92
(t, J = 7.2 Hz, 1 H), 2.29 (s, 6 H); HRMS (EI) calcd for C14H14 (M+)
182.1096, found 182.1097.
2-Methyl-1,1′-biphenyl (T 3−16, CAS no. 643-58-3): colorless
oil (lit.1h); 1H NMR (400 MHz, CDCl3, TMS) δ7.55 (d, J = 8.4 Hz, 2
C
dx.doi.org/10.1021/jo302791q | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
H), 7.41−7.46 (m, 3 H), 7.38 (d, J = 7.2 Hz, 1 H), 7.28−7.32 (m, 1
H), 7.20 (t, J = 7.6 Hz, 1 H), 7.16 (t, J = 9.2 Hz, 1 H), 3.46 (s, 3 H);
HRMS (EI) calcd for C13H12 (M+) 168.0939, found 168.0936.
2-Chloro-1,1′-biphenyl (T3−17, CAS no. 2051-60-7): white
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solid; mp 34−35 °C (lit.1h mp 34−35 °C); H NMR (400 MHz,
1
CDCl3, TMS) δ 7.59 (d, J = 8.4 Hz, 2 H), 7.40−7.49 (m, 4 H), 7.25−
7.36 (m, 3 H). HRMS (EI) calcd for C12H9Cl (M+) 188.0393, Found
188.0391.
2,6-Dimethyl-1,1′-biphenyl (T 3-18, CAS no. 3976-34-9):
colorless oil (lit.1f); 1H NMR (400 MHz, CDCl3, TMS) δ7.60 (d, J =
7.2 Hz, 3 H), 7.44 (t, J = 7.6 Hz, 3 H), 7.34 (t, J = 7.2 Hz, 1 H), 6.92
(t, J = 7.2 Hz, 1 H), 2.29 (s, 6 H); HRMS (EI) calcd for calcd for
C14H14 (M+) 182.1096, found 182.1097.
1-Phenylnaphthalene (T3−19, CAS no. 643-93-6): colorless oil
(lit.1e); 1H NMR (400 MHz, CDCl3, TMS) δ 7.90 (t, J = 8.0 Hz, 1 H),
7.59 (d, J = 8.4 Hz, 2 H), 7.48−7.53 (m, 3 H), 7.41−7.47 (m, 5 H),
7.33 (t, J = 7.2 Hz, 1 H); HRMS (EI) calcd for C16H12 (M+) 204.0939,
found 204.0937.
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2-Phenylnaphthalene (T3−20, CAS no. 612-94-2): white solid;
mp 96−97 °C (lit.1e mp 96−97 °C); H NMR (400 MHz, CDCl3,
1
TMS) δ 8.03 (s, 1 H), 7.84−7.93 (m, 3 H), 7.72 (t, J = 8.0 Hz, 3 H),
7.45−7.51 (m, 4 H), 7.37 (t, J = 7.2 Hz, 1 H); HRMS (EI) calcd for
C16H12 (M+) 204.0939, found 204.0936.
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ASSOCIATED CONTENT
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S
* Supporting Information
1H NMR spectra. This material is available free of charge via
the Internet at http://pubs.acs.org/.
AUTHOR INFORMATION
Corresponding Author
*Tel: +86-575-88345681. Fax: +86-575-88345681. E-mail:
qichenze@usx.edu.cn.
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Synlett 2006, 1891. (c) Behrends, M.; Savmarker, J.; Sjoberg, P. J. R.;
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Larhed, M. ACS Catal. 2011, 1, 1455. (d) Liu, J.; Zhou, X.; Rao, H.;
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2012, 53, 4347. (f) Wang, H.; Li, Y.; Zhang, R.; Jin, K.; Zhao, D.;
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A.; Li, C. J. Adv. Synth. Catal. 2011, 353, 1701. (h) Zhou, C.; Liu, Q.;
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This study was financially supported by the National Science
Foundation of China (Grant No. 21172149) and the Science
Technology Department of Zhejiang Province (Grant No.
2012R10014-15).
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