Nickel-Catalyzed Reaction of Aryl 2-Pyridyl Ethers with Silylzinc Chlorides: Silylation of Aryl 2-Pyridyl Ethers via Cleavage of the Carbon?Oxygen Bond

Article abstract of DOI:10.1002/adsc.201900949

Ni-catalyzed C?O(Py) bond activation and silylation of aryl 2-pyridyl ethers with silylzinc chlorides were carried out. This protocol allowed the 2-pyridyloxy group to be substituted by a silyl group with short reaction times, mild reaction conditions, and good compatibility of functional groups. (Figure presented.).

Full text of DOI:10.1002/adsc.201900949

Title: Nickel-Catalyzed Reaction of Aryl 2-Pyridyl Ethers with Silylzinc
Chlorides: Silylation of Aryl 2-Pyridyl Ethers via Cleavage of the
Carbon-Oxygen Bond
Authors: Ying-Ying Kong and Zhong-Xia Wang
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10.1002/adsc.201900949
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Nickel-Catalyzed Reaction of Aryl 2-Pyridyl Ethers with
Silylzinc Chlorides: Silylation of Aryl 2-Pyridyl Ethers via
Cleavage of the CarbonOxygen Bond
Ying-Ying Konga and Zhong-Xia Wanga,b,*
a
CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology
of China, Hefei, Anhui 230026, People's Republic of China. E-mail: zxwang@ustc.edu.cn.
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, People's Republic of China.
b
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. Ni-catalyzed C–O(Py) bond activation and functional groups.
silylation of aryl 2-pyridyl ethers with silylzinc chlorides
were carried out. This protocol allowed the 2-pyridyloxy
group to be substituted by a silyl group with short reaction
times, mild reaction conditions, and good compatibility of
Keywords: C-O bond activation; nickel catalysis;
silylation; aryl 2-pyridyl ether; silylzinc reagent
electrophiles with silylation reagents also attracts
considerable attention. Representative examples
include the coupling of aryl halides or esters with
silylboranes,[11] the coupling of aryl halides with
hydrosilanes or disilanes,[12] and aromatic C−H
silylation of arenes.[13] It is interesting to explore
silylation of aryl 2-pyridyl ethers with appropriate
silicon nucleophiles. Silylzinc reagents have better
Introduction
2-Pyridyloxy (OPy) group has been demonstrated to
be an excellent ortho directing group in transition-
metal-catalyzed
C−H
bond
functionalization
reactions of aromatic systems.[1] However, the
existence of the pyridyloxy group in the
functionalized products might limit the utility of the
products. Hence, developing methodology to remove
or functionalize the OPy moiety after directing C−H
functionalization is of great significance. Chatani et
al. reported first example of the OPy group
conversion from an aryl 2-pyridyl ether via rhodium-
or nickel-catalyzed C-OPy bond activation and
borylation.[2] Subsequently, we carried out
amination,[3] alkylation[4] and reduction[5] of aryl 2-
pyridyl ethers via nickel-catalyzed C-OPy bond
cleavage. Zeng et al. reported chromium-catalyzed
Kumada arylation of aryl 2-pyridyl ethers via C–OPy
bond activation.[6] Li et al. reported an example of
cross-coupling reaction of naphthyl 2-pyridyl ether
with Sc(CH2SiMe3)3(THF)2 under Ni(COD)2/PCy3
catalysis.[7] Although these significant achievements
have been made, the methods to remove or convert
the OPy group are still very limited.
compatibility
of
functional
groups
than
silylmagnesium and lithium reagents and showed
good reactivity in the reaction with alkyl or alkenyl
electrophiles.[14] Hence they were chosen as the
silylation reagents to perform the transformation of
aryl 2-pyridyl ethers. Herein we report the results.
Results and Discussion
2-([1,1'-Biphenyl]-4-yloxy)pyridine
(1a)
and
(dimethyl-(phenyl)silyl)zinc chloride (2a) were used
as the model substrates to screen the reaction
conditions.
Nickel
complexes
have
been
demonstrated to be effective in activation of the C-O
bonds of aryl pyridyl ethers. We also tested a series
of nickel complexes in this study. The readily
available nickel complexes including NiCl2(DME),
NiCl2(PPh3)2, and NiCl2(PMe3)2 were found to be
almost ineffective in THF at 60 °C (Table 1, entries
1-3). However, NiCl2(PCy3)2 showed good catalytic
activity in this transformation at the same solvent and
temperature as above, leading to the silylated product
3a in 84% yield (Table 1, entry 4). The nickel
complexes with didentate phosphine ligands such as
NiCl2(dppp) and NiCl2(dppf) exhibited very low
catalytic activity under the same conditions (Table 1,
On the other hand, aryl silanes are important
building blocks or synthetic intermediates in
medicinal chemistry and materials science.[8] Some
methodologies for the synthesis of arylsilanes have
been developed. The classic method for the synthesis
of arylsilanes is via the reaction of chlorosilanes with
arylmagnesium or aryllithium reagents.[9] Reaction of
silyllithium with aryl halides was reported recently.[10]
Transition-metal-catalyzed reaction of aromatic
1
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10.1002/adsc.201900949
Advanced Synthesis & Catalysis
Table 1. Optimization of reaction conditions[a]
17-19). The reaction time was also examined. Longer
reaction time than 12 h did not improve the reaction
results. Further tests demonstrated that the reaction
can be completed in 1 h (Table 1, entries 20-22).
Attempt to further improve the product yield, 15
mol% catalyst were employed. The result showed
that the reaction gave the same product yield as that
employing 10 mol% catalyst. When 5 mol% catalyst
was used, a marked yield decrease was observed
(Table 1, entries 23 and 24). Finally, in the absence of
any nickel catalysts, the reaction gave only trace
amount of product (Table 1, entry 25).
Entry [Ni]
Solvent
Yield (%)[b]
1
NiCl2(DME)
THF
3
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
NiCl2(PPh3)2
NiCl2(PMe3)2
NiCl2(PCy3)2
NiCl2(dppp)
NiCl2(dppf)
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
NiCl2(PCy3)2
-
THF
THF
THF
THF
THF
Et2O
dioxane
toluene
DMSO
NMP
DMA
NMP/THF(1:1)
trace
trace
84
6
3
trace
4
trace
trace
20
Under the optimized conditions, reaction of
various aryl 2-pyridyl ethers with PhMe2SiZnCl (2a)
was tested. Like 2-(biphenyl-4-yloxy)pyridine, both
2-(biphenyl-3-yloxy)pyridine and 2-(biphenyl-2-
yloxy)pyridine also reacted smoothly with 2a, but
they led to the corresponding products in lower yields
than 2-(biphenyl-4-yloxy)pyridine (Table 2, 3ab and
3ac). 2-Phenoxypyridine and 4-alkyl-substituted
phenyl 2-pyridyl ethers including 2-(4-benzyl
25
24
DMA/THF(1:1) 27
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
78[c]
phenoxy)pyridine
and
2-(4-tert-butylphenoxy)
69[d]
85[e]
pyridine displayed similar reactivity to 2-(biphenyl-3-
yloxy)pyridine. Their reaction with PhMe2SiZnCl
gave the desired products in 61% to 69% yields
(Table 2, 3b-3d). (E)-2-(4-Styrylphenoxy)pyridine
showed markedly higher reactivity than the 4-alkyl-
substituted phenyl 2-pyridyl ethers (Table 2, 3e). A
series of alkoxy-substituted phenyl 2-pyridyl ethers
were also tested (Table 2, 3e-3h). They showed
similar reactivity to the alkyl-substituted phenyl 2-
pyridyl ethers. In the reactions the alkoxy groups on
the aromatic rings were tolerated. Reaction of 2-(2-
methoxyphenoxy)pyridine gave the product in lower
yield compared with that of 2-(3-methoxy
70[f]
73[g]
85[h]
84[i]
85(82)[j]
85[c,k]
27[l]
25
trace
[a]
Unless otherwise stated, the reactions were carried out
according to the conditions indicated by the above
equation; 0.2 mmol of 1a and 0.22 mmol of PhMe2SiZnCl
(2a) were employed. 2a was prepared by reaction of
PhMe2SiLi with an equimolar of ZnCl2 in THF.
phenoxy)pyridine
and
2-(4-methoxyphenoxy)
[b]
GC
pyridine (Table 2, 3fa-3fc). This is ascribed to steric
hindrance of the ortho-MeO group in 2-(2-
methoxyphenoxy)pyridine. N,N-Dimethyl-4-(pyridin-
2-yloxy)aniline exhibited lower reactivity than the
alkoxy-substituted phenyl 2-pyridyl ethers possibly
due to strong electron donating property of the Me2N
group in N,N-dimethyl-4-(pyridin-2-yloxy)aniline
(Table 2, 3j). Acetamido-substituted phenyl 2-pyridyl
yield using dodecane as an internal standerd; isolated yield
[c]
is shown in parentheses.
1.25 equiv of 2a were
[d]
[e]
employed. 1.5 equiv of 2a were employed.
reaction was carried out at 100 °C.
The reaction was carried out at
25 °C. The reaction time was 24 h. The reaction time
The
[f]
The reaction was
[g]
carried out at 40 °C.
[h]
[i]
[j]
[k]
was 4 h.
The reaction time was 1 h.
15 mol% of
[l]
NiCl2(PCy3)2 was employed.
was employed.
5 mol% of NiCl2(PCy3)2
ethers
including
N-(4-(pyridin-2-yloxy)phenyl)
acetamide and N-methyl-N-(4-(pyridin-2-yloxy)-
phenyl)acetamide also showed higher reactivity than
N,N-dimethyl-4-(pyridin-2-yloxy)aniline (Table 2, 3k
and 3l). It seems that the acidic proton of the
MeC(O)NH group in N-(4-(pyridin-2-yloxy)phenyl)
acetamide did not have an effect on the coupling
reaction. Three aryl 2-pyridyl ethers with a fused
aromatic system including 2-(naphthalen-2-yloxy)
pyridine, 2-(naphthalen-1-yloxy)pyridine and 6-
(pyridin-2-yloxy)quinoline were tested and their
reaction with 2a resulted in the corresponding
products in 75%, 57% and 37% yields, respectively
(Table 2, 3m-3o). It is a little surprise that reaction of
6-(pyridin-2-yloxy)quinoline gave the lowest product
yield for unclear reason. 2,2'-Oxydipyridine was
demonstrated to react with 2a to afford 2-
(dimethyl(phenyl)silyl)pyridine in 74% yield (Table 2,
entries 5 and 6). Next, solvents were screened. Et2O,
1,4-dioxane, toluene and DMSO were not suitable
solvents for this reaction. Only trace amount of
products were observed when the reaction was run in
these solvents (Table 1, entries 7-10). When the
reaction was respectively carried out in NMP, DMA,
or mixed solvents NMP/THF (1:1) and DMA/THF
(1:1), the desired product were achieved in 20-27%
yields (Table 1, entries 11-14). Then we
demonstrated that higher 2a loading than 1.1
equivalents cannot increase the product yield (Table 1,
entries 15 and 16). The reaction performed at 100 °C
gave almost same yield as that at 60 °C. However,
when the reaction was run at lower temperature than
60 °C, the product yields decreased (Table 1, entries
2
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10.1002/adsc.201900949
Advanced Synthesis & Catalysis
3p). However, in the reaction of aryl 2-pyridyl ethers
with 2a no products via C(Py)-O bond cleavage were
observed. Other electron-poor aryl 2-pyridyl ethers
2-(4-Fluorophenoxy)pyridine, 1-(4-(pyridin-2-yloxy)
phenyl)ethan-1-one and N,N-diethyl-4-(pyridin-2-
yloxy)benzamide led to relatively low product yields.
The other compounds led to good or very good yield
in the transformation. The relatively low product
yield of reaction of 1-(4-(pyridin-2-yloxy)phenyl)
ethan-1-one with 2a was probably due to side
reaction of MeC(O) group with 2a. The reaction of 2-
including
2-((4'-fluoro-[1,1'-biphenyl]-4-yl)oxy)
pyridine, 2-(4-fluorophenoxy)pyridine, phenyl(4-
(pyridin-2-yloxy)phenyl)methanone, 1-(4-(pyridin-2-
yloxy)phenyl)ethan-1-one, isopropyl 4-(pyridin-2-
yloxy)benzoate,
benzoate, methyl 4-(pyridin-2-yloxy)benzoate and
N,N-diethyl-4-(pyridin-2-yloxy)benzamide were
tert-butyl
4-(pyridin-2-yloxy)
(4-fluorophenoxy)pyridine
and
N,N-diethyl-4-
(pyridin-2-yloxy)benzamide with 2a led to low
examined under the same conditions (Table 2, 3q-3x). product yields for unclear reasons. Two ortho-
electron-withdrawing-group-substituted phenyl 2-
Table 2. Scope of aryl 2-pyridyl ethers[a,b]
pyridyl
ethers,
1-(2-(pyridin-2-yloxy)phenyl)
ethanone and ethyl 2-(pyridin-2-yloxy)benzoate, also
reacted smoothly with 2a to afford the desired
products in 71% and 86% yields, respectively (Table
2, 3y and 3z). From above reaction data it seems that
the ethers with large conjugated aromatic systems or
electron-poor aromatic systems have better reactivity
in the coupling. The steric effect plays some role. The
ethers with sterically hindered aryl groups led to low
product yields (Table 2, 3ac, 3fc and 3n). In addition,
in each reaction small amounts of homocoupling
products of the aryl groups and other unidentified
byproducts could be observed by TLC. We could
hardly find remained starting materials.
Other silylzinc reagents were also tested.
Me3SiZnCl was not a suitable nucleophilic reagent in
this transformation. Ph2MeSiZnCl showed similar
reactivity to PhMe2SiZnCl under the same conditions
as above. Reaction of Ph2MeSiZnCl with conjugated
aryl 2-pyridyl ether, 2-([1,1'-biphenyl]-4-yloxy)
pyridine, or electron-poor aryl 2-pyridyl ether,
isopropyl 4-(pyridin-2-yloxy)benzoate, resulted in the
desired products in very good yields (Table 3, 4a and
4b). Reaction of Ph2MeSiZnCl with electron-rich aryl
2-pyridyl ether, 2-(4-methoxyphenoxy)pyridine, led
to the coupling product in markedly lower yield
(Table 3, 4c). In the reactions of Ph2MeSiZnCl we
also observed small amounts of homocoupling
byproducts. Under the same conditions, Ph3SiZnCl
exhibited different reactivity. Reaction of Ph3SiZnCl
with 2-([1,1'-biphenyl]-4-yloxy)pyridine gave the
desired coupling product in 58% yield (Table 3, 5a).
A small amount of homocoupling product of 2-([1,1'-
biphenyl]-4-yloxy)pyridine was observed. Reaction
of Ph3SiZnCl with 2-(4-methoxy-phenoxy)pyridine
or isopropyl 4-(pyridin-2-yloxy)benzoate gave the
desired products in 33% and 25% yields, respectively,
along with homocoupling species of the aryl 2-
pyridyl ethers in 32% and 30% yields, respectively
(Table 3, 5b and 5c). Attempts to improve the
reaction by using Ph3SiLi, (Ph3Si)2Zn or (Ph3Si)3ZnLi
as the nucleophiles were unsuccessful. Reaction of
these nucleophilic reagents with 2-(4-methoxy
phenoxy)pyridine or 2-(biphenyl-4-yloxy)pyridine
under the optimized conditions gave the
corresponding silylated products in low yields (11-
29%) (Table S1 in the Supporting Information).
[a]
The reactions were carried out according to the
conditions indicated by the above equation. 0.2 mmol 2-
([1,1-biphenyl]-4-yloxy)pyridine and 1.1 equiv of
PhMe2SiZnCl (2a) were employed; 2a was prepared by
reaction of PhMe2SiLi with an equimolar of ZnCl2 in THF.
[b] Isolated yield was reported. The yield was calculated
[c]
based
on
the
weight
of
the
mixture
of
dimethyldiphenylsilane and the desired product and the
integral ratio of H NMR spectrum of the mixture.
Reaction time was 2 h.
As indicated in the introduction, 2-pyridyloxy
group is one of the most effective directing groups
which could facilitate various aromatic functionaliza-
1
[d]
3
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10.1002/adsc.201900949
Advanced Synthesis & Catalysis
Table 3. Reaction of aryl 2-pyridyl ethers with
Preliminary study on the plausible reaction
pathway was carried out. Under the standard
conditions, 1 equiv of 1,1-diphenylethylene additive
had no influence on the reaction results of 2-
(biphenyl-4-yloxy)pyridine with 2a; 80% yield of the
coupling product was isolated. This ruled out the
possibility of a free radical process. A combination of
Ni(COD)2 (10 mol%) and PCy3 (20 mol%) was
demonstrated to be as effective as Ni(PCy3)2Cl2 (10
mol%) to catalyze the reaction of 2-(biphenyl-4-
yloxy)pyridine with 2a. Hence we surmised that the
catalytic reaction proceeded through a Ni(0)/Ni(II)
cycle. We also studied the reaction process by 31P
NMR spectroscopy. Reaction of Ni(COD)2 with 2
equiv of PCy3 formed a nickel complex which
displayed a 31P NMR signal at  45.3 ppm, along with
a signal of PCy3 at  9.77 ppm.[15] After reaction of
above solution with an equiv of 2-(biphenyl-4-yloxy)
pyridine a new 31P NMR spectral signal at  30.3
ppm appeared. This new signal might be that of the
oxidative addition intermediate of the Ni-PCy3
complex with 2-(biphenyl-4-yloxy)pyridine.[16] The
results further supported a Ni(0)/Ni(II) process. In
addition, reaction of 3-([1,1'-biphenyl]-4-yloxy)
pyridine with 2a cannot occur under the standard
conditions. This experimental fact implies that the
chelation assistance of pyridine might help the
catalyst to exclusively break the C–OPy bond. Based
on the above experimental facts, a possible catalytic
cycle is proposed in Scheme 2.
Ph2MeSiZnCl and Ph3SiZnCl[a,b]
[a] Unless otherwise stated, the reactions were carried out
according to the conditions indicated by the above
equation; 0.2 mmol 2-([1,1'-biphenyl]-4-yloxy)pyridine
and 1.1 equiv of 2a were employed. Ph2MeSiZnCl and
Ph3SiZnCl were prepared by reaction of the corresponding
silyllithium with an equimolar amount of ZnCl2. [b] Unless
[c]
otherwise stated, yield reported was isolated yield. The
yield was calculated based on the weight of the mixture of
[1,1'-biphenyl]-4-yl(methyl)diphenylsilane and 1,2-di-
methyl-1,1,2,2-tetraphenyldisilane and the integral ratio of
[d]
1H NMR spectrum of the mixture. 4,4'-Dimethoxy-1,1'-
[e]
biphenyl was formed in 32% yield.
Diisopropyl [1,1'-
biphenyl]-4,4'-dicarboxylate was formed in 30% yield.
tion reactions. In this study we performed the
sequential OPy-directed ortho C-H functionalization
and removal of the directing group to demonstrate the
practicability of the methodology developed in this
work. Both 2-(2-methoxyphenoxy)pyridine and 2-
(biphenyl-2-yloxy)pyridine prepared according to
literature procedures[1b,h] can be successfully silylated
via nickel-catalyzed reaction of PhMe2SiZnCl with
the corresponding aryl 2-pyridyl ethers (Scheme 1).
Scheme 2. Proposed catalytic cycle.
On the other hand, the solution formed from the
reaction of Ni(COD)2 with 2 equiv of PCy3 was
treated with an equiv of PhMe2SiZnCl to lead to
disappearance of the signal of Ni(COD)2-PCy3
complex and appearance of two new 31P NMR signals
at  52.6 and 0.75 ppm, respectively. The emerging
signals might result from nickel(0) ate complexes
such
as
[PhMe2SiNi(PCy3)2]ZnCl+
and
[PhMe2SiNi(PCy3)(COD)]ZnCl+.[17,18] Hence it is
possible that another catalytic cycle operates
concurrently (Scheme 3).[19]
Scheme 1. The sequential reaction.
4
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10.1002/adsc.201900949
Advanced Synthesis & Catalysis
High-resolution mass spectra (HRMS) were acquired on a
Thermo Fisher LTQ Orbitrap XL mass spectrometer.
Conclusion
In summary, we carried out the reaction of aryl 2-
pyridyl ethers with silylzinc reagents via Ni-catalyzed
C-O(Py) bond cleavage under mild conditions,
providing the corresponding silylated arenes in
moderate to good yields. The method suits for a wide
scope of aryl 2-pyridyl ethers including those with
electron-poor and electron-rich aryl groups and
nitrogen-containing heteroaryl groups. A range of
functional groups on the aromatic rings including
alkoxy, alkenyl, Me2N, F, C(O)R, COOR, C(O)NEt2
and MeC(O)NH groups can be tolerated. Both
PhMe2SiZnCl and Ph2MeSiZnCl were suitable
silylation reagents. Reaction of Ph3SiZnCl resulted in
low yields due to homocoupling of aryl 2-pyridyl
ethers and Me3SiZnCl cannot be used in this
transformation.
General procedure for the catalytic coupling of aryl 2-
pyridyl ethers with silylzinc reagents
A Schlenk tube was charged with NiCl2(PCy3)2 (13.8 mg,
0.020 mmol), aryl 2-pyridyl ethers (0.20 mmol) and THF
(1.4 mL). To the stirred mixture was added PhMe2SiZnCl
solution (0.6 mL, 0.37 M solution in THF, 0.22 mmol).
The resultant mixture was stirred at 60 °C for 1 h and then
cooled to room temperature. A 20% aqueous solution of
NH4Cl (10 mL) was added. The mixture was extracted
with ethyl acetate (3 × 10 mL). The combined organic
phases were dried over anhydrous Na2SO4, concentrated by
rotary
evaporation,
and
purified
by
column
chromatography (silica gel).
[1,1'-Biphenyl]-4-yldimethyl(phenyl)silane
(3aa):[23]
Yield: 47.5 mg (82%); white solid. 1H NMR (400 MHz,
CDCl3): δ 7.73-7.60 (m, 8H), 7.54-7.48 (m, 2H), 7.47-7.37
(m, 4H), 0.67 (s, 6H). 13C NMR (101 MHz, CDCl3): δ
142.0, 141.2, 138.3, 137.1, 134.8, 134.3, 129.3, 128.9,
128.0, 127.5, 127.3, 126.3, 2.2.
[1,1'-Biphenyl]-3-yldimethyl(phenyl)silane
(3ab):[10b]
1
Yield: 39.1 mg (68%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.74 (s, 1H), 7.63-7.54 (m, 5H), 7.53 (d, J = 7.2
Hz, 1H), 7.45 (t, J = 7.5 Hz, 3H), 7.40-7.32 (m, 4H), 0.60
(s, 6H). 13C NMR (101 MHz, CDCl3): δ 141.6, 140.7,
138.9, 138.3, 134.3, 133.3, 133.1, 129.3, 128.9, 128.3,
128.2, 128.0, 127.4, 127.3, 2.2. HR-MS (ESI): m/z =
288.1330, calcd. for C20H20Si ([M]+): 288.1329.
[1,1'-Biphenyl]-2-yldimethyl(phenyl)silane
(3ac):[24]
1
Yield: 28.6 mg (50%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.62 (d, J = 7.4 Hz, 1H), 7.44-7.17 (m, 11H),
7.11-7.05 (m, 2H), 0.17 (s, 6H). 13C NMR (101 MHz,
CDCl3): δ 149.7, 144.2, 140.2, 136.6, 135.9, 134.1, 130.0,
129.8, 129.6, 129.1, 128.8, 128.0, 127.8, 127.7, 127.1,
126.4, 1.1.
(4-Benzylphenyl)dimethyl(phenyl)silane (3c): Yield:
41.1 mg (68%); colorless oil. 1H NMR (400 MHz, CDCl3):
δ 7.57-7.51 (m, 2H), 7.46 (d, J = 7.9 Hz, 2H), 7.39-7.33 (m,
3H), 7.31-7.27 (m, 2H), 7.25-7.17 (m, 5H), 3.99 (s, 2H),
0.55 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 142.2, 141.0,
138.5, 135.6, 134.5, 134.3, 129.2, 129.1, 128.6, 128.5,
127.9, 126.2, 42.1, 2.2. HR-MS (ESI): m/z = 302.1486,
calcd. for C21H22Si ([M]+): 302.1485.
Scheme 3. Another possible reaction pathway.
Experimental Section
General
(E)-Dimethyl(phenyl)(4-styrylphenyl)silane (3e): Yield:
1
54.1 mg (86%); white solid. H NMR (400 MHz, CDCl3):
δ 7.63-7.52 (m, 8H), 7.45-7.37 (m, 5H), 7.34-7.27 (m, 1H),
7.20 (d, J = 16.4 Hz, 1H), 7.15 (d, J = 16.4 Hz, 1H), 0.62
(s, 6H). 13C NMR (101 MHz, CDCl3): δ 138.3, 138.1,
137.8, 137.4, 134.7, 134.3, 129.3, 129.2, 128.8, 128.7,
128.0, 127.8, 126.7, 126.0, 2.2. HR-MS (ESI): m/z =
314.1484, calcd. for C22H22Si ([M]+): 314.1485 .
All reactions were performed under nitrogen atmosphere
using standard Schlenk and vacuum line techniques.
Toluene, THF and Et2O were purified by JC Meyer
Phoenix Solvent Systems. 1,4-Dioxane was distilled under
nitrogen over sodium and degassed prior to use. DMSO,
DMAc and NMP were dried over 4 Å molecular sieves,
fractionally distilled under reduced pressure, and stored
under nitrogen atmosphere. PhMe2SiCl, Ph2MeSiCl,
Ph3SiCl, NiCl2(PPh3)2, and NiCl2(PCy3)2 were purchased
from Energy Chemical. Ni(COD)2 was purchased from
Alfa Aesar. PCy3 was purchased from J＆K Scientific Ltd.
(4-Methoxyphenyl)dimethyl(phenyl)silane
(3fa):[12b]
1
Yield: 34.9 mg (71%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.55-7.49 (m, 2H), 7.46 (d, J = 8.5 Hz, 2H),
7.39-7.32 (m, 3H), 6.92 (d, J = 8.5 Hz, 2H), 3.82 (s, 3H),
0.53 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 160.6, 138.8,
135.8, 134.3, 129.1, 127.9, 113.7, 55.2, 2.1.
Aryl
2-pyridyl
ethers,[2a,20]
NiCl2(PMe3)2,[21]
NiCl2(dppp),[21] NiCl2(dppf),[21] and silylzinc reagents[14b]
were prepared according to the literature procedures. The
concentration of the silylzinc solution was titrated using
Knochel’s method.[22] Other chemicals were obtained from
commercial vendors. NMR spectra were recorded on a
Bruker av400 spectrometer at 25 °C. The chemical shifts
of the 1H NMR spectra were referenced to TMS or internal
solvent resonances and the chemical shifts of the 13C NMR
spectra were referenced to internal solvent resonances.
(2-Methoxyphenyl)dimethyl(phenyl)silane (3fb): Yield:
31.3 mg (64%); colorless oil. 1H NMR (400 MHz, CDCl3):
δ 7.61-7.53 (m, 2H), 7.40-7.32 (m, 4H), 7.28 (dd, J = 7.2,
1.6 Hz, 1H), 6.93 (t, J = 7.3 Hz, 1H), 6.84 (d, J = 8.2 Hz,
1H), 3.75 (s, 3H), 0.56 (s, 6H). 13C NMR (101 MHz,
CDCl3): δ 164.6, 139.1, 136.1, 134.3, 131.2, 128.8, 127.7,
126.2, 120.6, 109.9, 55.2, -2.1. HR-MS (ESI): m/z =
243.1196, calcd. for C15H19OSi ([M+H]+): 243.1200.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900949
Advanced Synthesis & Catalysis
(3-Methoxyphenyl)dimethyl(phenyl)silane (3fc):[11a,25]
(d, J = 3.0 Hz, 1H), 8.14 (d, J = 8.2 Hz, 1H), 8.08 (d, J =
8.4 Hz, 7.98 (s, 1H), 7.84 (d, J = 8.4 Hz, 1H), 7.59-7.52 (m,
2H), 7.44-7.34 (m, 4H), 0.65 (s, 6H). 13C NMR (101 MHz,
CDCl3): δ = 151.0, 148.8, 137.8, 137.3, 136.3, 134.9, 134.4,
134.3, 129.5, 128.6, 128.1, 127.9, 121.3, 2.2. HR-MS
(ESI): m/z = 264.1195, calcd. for C17H18NSi ([M+H]+):
264.1203.
1
Yield: 34.8 mg (70%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.57-7.50 (m, 2H), 7.39-7.27 (m, 4H), 7.11 (d, J
= 7.2 Hz, 1H), 7.06 (d, J = 2.6 Hz, 1H), 6.91 (dd, J = 8.2,
2.6 Hz, 1H), 3.80 (s, 3H), 0.55 (s, 6H). 13C NMR (101
MHz, CDCl3): δ 159.1, 140.0, 138.2, 134.3, 129.3, 129.2,
127.9, 126.6, 120.0, 114.3, 55.2, 2.3.
(4-(Benzyloxy)phenyl)dimethyl(phenyl)silane
(3g):
2-(Dimethyl(phenyl)silyl)pyridine (3p):[28] Yield: 31.6
1
1
Yield: 40.6 mg (64%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.57-7.51 (m, 2H), 7.49-7.30 (m, 10H), 7.00 (d,
J = 8.6 Hz, 2H), 5.09 (s, 2H), 0.55 (s, 6H). 13C NMR (101
MHz, CDCl3): δ 159.9, 138.8, 137.1, 135.8, 134.3, 129.5,
129.2, 128.7, 128.1, 127.9, 127.6, 114.6, 69.9, 2.1. HR-
MS (ESI): m/z = 319.1513, calcd. for C21H23OSi ([M+H]+):
319.1513.
mg (74%); pale yellow oil. H NMR (400 MHz, CDCl3): δ
8.81 (dt, J = 4.8, 1.2 Hz, 1H), 7.63-7.58 (m, 2H), 7.55 (dt,
J = 7.6, 1.7 Hz, 1H), 7.44 (dt, J = 7.5, 1.1 Hz, 1H), 7.40-
7.35 (m, 3H), 7.22-7.17 (m, 1H), 0.63 (s, 6H). 13C NMR
(101 MHz, CDCl3): δ 166.7, 150.4, 137.4, 134.4, 134.1,
129.9, 129.4, 128.0, 123.0, 3.0.
(4'-Fluoro-[1,1'-biphenyl]-4-yl)dimethyl(phenyl)silane
1
Dimethyl(4-phenoxyphenyl)(phenyl)silane
(3h):[10b]
(3q): Yield: 43.3 mg (71%); white solid. H NMR (400
1
Yield: 40.5 mg (67%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.59-7.53 (m, 2H), 7.49 (d, J = 8.5 Hz), 7.42-
7.32 (m, 5H), 7.13 (t, J = 7.4 Hz, 1H), 7.09-7.03 (m, 2H),
7.00 (d, J = 8.5 Hz), 0.57 (s, 6H). 13C NMR (101 MHz,
CDCl3): δ 158.6, 156.8, 138.4, 135.9, 134.3, 132.2, 129.9,
129.2, 128.0, 123.6, 119.5, 118.1, 2.1. HR-MS (ESI): m/z
= 305.1351, calcd. for C20H21OSi ([M+H]+): 319.1513.
MHz, CDCl3): δ 7.63-7.51 (m, 8H), 7.41-7.36 (m, 3H),
7.13 (t, J = 8.7 Hz, 2H), 0.59 (s, 6H). 13C NMR (101 MHz,
CDCl3): δ 162.7 (d, J = 245.0 Hz), 141.0, 138.2, 137.3 (d,
J = 3.1 Hz), 137.2, 134.9, 134.3, 129.3, 128.8 (d, J = 8.1
Hz), 128.0, 126.5, 115.8 (d, J = 21.5 Hz), 2.2. 19F NMR
(376 MHz, CDCl3): δ 115.54. HR-MS (ESI): m/z =
306.1235, calcd. for C20H19FSi ([M]+): 306.1235.
Benzo[d][1,3]dioxol-5-yldimethyl(phenyl)silane
(3i):
(4-(Dimethyl(phenyl)silyl)phenyl)(phenyl)methanone
1
1
Yield: 31.7 mg (62%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.58-7.49 (m, 2H), 7.42-7.32 (m, 3H), 7.02 (d, J
= 7.6 Hz, 1H) , 6.98 (s, 1H), 6.86 (d, J = 7.6 Hz, 1H), 5.94
(3s): Yield: 52.4 mg (84%); colorless oil. H NMR (400
MHz, CDCl3): δ 7.86-7.80 (m, 2H), 7.77 (d, J = 8.0 Hz,
2H), 7.65 (d, J = 8.0 Hz, 2H), 7.62-7.53 (m, 3H), 7.49 (t, J
(s, 2H), 0.54 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 148.6, = 7.6 Hz, 2H), 7.44-7.35 (m, 3H), 0.62 (s, 6H). 13C NMR
147.5, 138.4, 134.2, 131.3, 129.2, 128.4, 128.0, 113.6,
108.7, 100.7, 2.0. HR-MS (ESI): m/z = 257.0989, calcd
for C15H17O2Si ([M+H]+): 257.0992.
(101 MHz, CDCl3): δ 197.0, 144.2, 138.1, 137.6, 137.4,
134.3, 134.2, 132.6, 130.2, 129.5, 129.2, 128.4, 128.1, 2.4.
HR-MS (ESI): m/z = 317.1352, calcd. for C21H21OSi
([M+H]+): 317.1356.
4-(Dimethyl(phenyl)silyl)-N,N-dimethylaniline (3j):[26]
1
Yield: 22.3 mg (44%); pale yellow solid. H NMR (400
1-(4-(Dimethyl(phenyl)silyl)phenyl)ethan-1-one (3t):[29]
1
MHz, CDCl3): δ 7.58-7.52 (m, 2H), 7.41 (d, J = 8.6 Hz,
2H), 7.38-7.32 (m, 3H), 6.75 (d, J = 8.5 Hz, 2H), 2.97 (s,
6H), 0.53 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 151.2,
139.5, 135.4, 134.3, 128.9, 127.8, 123.1, 112.0, 40.3, 2.0.
Yield: 33.6 mg (67%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.92 (d, J = 8.2 Hz, 2H), 7.63 (d, J = 8.2 Hz,
2H), 7.54-7.49 (m, 2H), 7.42-7.34 (m, 3H), 2.60 (s, 3H),
0.59 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 198.6, 145.2,
137.5, 137.3, 134.5, 134.3, 129.5, 128.1, 127.4, 26.8, 2.5.
N-(4-(Dimethyl(phenyl)silyl)phenyl)acetamide (3k):[12g]
1
Yield: 31.8 mg (60%); white solid. H NMR (400 MHz,
Isopropyl 4-(dimethyl(phenyl)silyl)benzoate (3u): Yield:
1
CDCl3): δ 7.55-7.43 (m, 6H), 7.40-7.30 (m, 3H), 7.21 (b,
1H), 2.17 (s, 3H), 0.53 (s, 6H). 13C NMR (101 MHz,
CDCl3): δ 168.4, 138.8, 138.4, 135.2, 134.3, 133.9, 129.2,
127.9, 119.2, 24.8, 2.2.
50.5 mg (85%); pale yellow oil. H NMR (400 MHz,
CDCl3): δ 8.02 (d, J = 8.2 Hz, 2H), 7.61 (d, J = 8.2 Hz,
2H), 7.55-7.49 (m, 2H), 7.41-7.34 (m, 3H), 5.32-5.23 (m,
1H), 1.38 (d, J = 6.3 Hz, 6H), 0.59 (s, 6H). 13C NMR (101
MHz, CDCl3): δ 166.3, 144.4, 137.5, 134.3, 134.2, 131.5,
129.5, 128.6, 128.0, 68.4, 22.1, 2.4. HR-MS (ESI): m/z =
299.1453, calcd. for C18H23O2Si ([M+H]+): 299.1462.
N-(4-(Dimethyl(phenyl)silyl)phenyl)-N-
methylacetamide (3l): Yield: 33.8 mg (60%); white solid.
1H NMR (400 MHz, CDCl3): δ 7.59-7.50 (m, 4H), 7.42-
7.33 (m, 3H), 7.16 (d, J = 7.9 Hz, 2H), 3.26 (s, 3H), 1.89 (s, tert-Butyl 4-(dimethyl(phenyl)silyl)benzoate (3v): Yield:
3H), 0.57 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 170.6,
52.3 mg (84%); colorless oil. 1H NMR (400 MHz, CDCl3):
145.3, 138.3, 137.6, 135.6, 134.2, 129.5, 128.0, 126.4, 37.2, δ 7.95 (d, J = 8.2 Hz, 2H), 7.58 (d, J = 8.2 Hz, 2H), 7.53-
22.6, 2.3. HR-MS (ESI): m/z = 284.1464, calcd for
7.47 (m, 2H), 7.40-7.32 (m, 3H), 1.59 (s, 9H), 0.57 (s, 6H).
13C NMR (101 MHz, CDCl3): δ 166.0, 144.1, 137.6, 134.3,
134.2, 132.6, 129.4, 128.5, 128.0, 81.1, 28.3, 2.4. HR-MS
(ESI): m/z = 313.1609, calcd. for C19H25O2Si ([M+H]+):
313.1618.
C17H22ONSi ([M+H]+): 284.1465.
Dimethyl(naphthalen-2-yl)(phenyl)silane (3m):[27] Yield:
39.3 mg (75%); colorless oil. 1H NMR (400 MHz, CDCl3):
δ 8.05 (s, 1H), 7.88-7.81 (m, 3H), 7.64-7.56 (m, 3H), 7.53-
7.47 (m, 2H), 7.42-7.35 (m, 3H), 0.66 (s, 6H). 13C NMR
(101 MHz, CDCl3): δ 138.3, 135.8, 135.0, 134.4, 133.9,
133.0, 130.5, 129.3, 128.2, 128.0, 127.8, 127.2, 126.5,
126.0, 2.2.
Methyl 4-(dimethyl(phenyl)silyl)benzoate (3w):[11a]
1
Yield: 43.4 mg (81%); colorless oil. H NMR (400 MHz,
CDCl3): δ 8.00 (d, J = 8.2 Hz, 2H), 7.60 (d, J = 8.2 Hz,
2H), 7.54-7.48 (m, 2H), 7.41-7.33 (m, 3H), 3.92 (s, 3H),
0.58 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 167.4, 144.8,
137.5, 134.29, 134.27, 130.7, 129.5, 128.7, 128.1, 52.3, 
2.4.
Dimethyl(naphthalen-1-yl)(phenyl)silane (3n): Yield:
29.9 mg (57%); colorless oil. 1H NMR (400 MHz, CDCl3):
δ 8.00-7.85 (m, 3H), 7.76 dd, J = 6.8, 1.0 Hz, 1H), 7.60-
7.55 (m, 2H), 7.53-7.43 (m, 2H), 7.42-7.33 (m, 4H), 0.74
(s, 6H). 13C NMR (101 MHz, CDCl3): δ 139.0, 137.1,
135.9, 134.8, 134.3, 133.6, 130.4, 129.2, 129.1, 128.7,
128.0, 125.8, 125.5, 125.2, 0.8. HR-MS (ESI): m/z =
262.1172, calcd. for C18H18Si ([M]+): 262.1172.
4-(Dimethyl(phenyl)silyl)-N,N-diethylbenzamide (3x):
1
Yield: 33.6 mg (54%); colorless oil. H NMR (400 MHz,
CDCl3): δ 7.56-7.49 (m, 4H), 7.40-7.31 (m, 5H), 3.62-3.49
(m, 2H), 3.32-3.19 (m, 2H), 1.32-1.19 (m, 3H), 1.17-1.05
(m, 3H), 0.56 (s, 6H). 13C NMR (101 MHz, CDCl3): δ
171.4, 139.7, 137.9, 137.8, 134.32, 134.29, 129.4, 128.0,
125.6, 43.3, 39.3, 14.4, 13.0, 2.4. HR-MS (ESI): m/z =
312.1768, calcd for C19H25NOSi ([M+H]+): 312.1778.
6-(Dimethyl(phenyl)silyl)quinolone (3o): Yield: 19.7 mg
1
(37%); colorless oil. H NMR (400 MHz, CDCl3): δ 8.92
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900949
Advanced Synthesis & Catalysis
1-(2-(Dimethyl(phenyl)silyl)phenyl)ethanone (3y): Yield: 64.3 mg (52%), colorless oil. 1H NMR (400 MHz, CDCl3):
35.6 mg (70%); colorless oil. 1H NMR (400 MHz, CDCl3):
δ 7.91-7.84 (m, 1H), 7.65-7.60 (m, 1H), 7.54-7.45 (m, 4H),
7.34-7.28 (m, 3H), 2.49 (s, 3H), 0.57 (s, 6H). 13C NMR
(101 MHz, CDCl3): δ 200.0, 142.9, 140.6, 140.1, 137.5,
134.0, 131.7, 129.8, 129.3, 128.4, 127.6, 27.1, 0.9. HR-
MS (EI): m/z = 239.0887, calcd for C15H15OSi ([M-Me]+):
239.0887.
δ 8.10 (dd, J = 1.4, 4.9 Hz, 1H), 7.56-7.49 (m, 1H), 7.49-
7.42 (m, 3H), 7.37 (dt, J = 1.7, 7.6 Hz, 1H), 7.32-7.25 (m,
3H), 7.25-7.19 (m, 1H), 7.17 (dd, J = 1.0, 8.0 Hz, 1H),
6.88-6.81 (m, 1H), 6.73 (d, J = 8.3 Hz, 1H). 13C NMR (101
MHz, CDCl3): δ 163.9, 151.0, 147.7, 139.2, 137.9, 134.8,
131.3, 129.2, 128.7, 128.1, 127.2, 125.4, 122.8, 118.1,
111.4.
Ethyl 2-(dimethyl(phenyl)silyl)benzoate (3z): Yield:
48.7 mg (86%); colorless oil. 1H NMR (400 MHz, CDCl3):
δ 8.02-7.96 (m, 1H), 7.60-7.55 (m, 1H), 7.52-7.41 (m, 4H),
7.36-7.28 (m, 3H), 4.12 (q, J = 7.2 Hz, 2H), 1.19 (t, J = 7.2
Hz, 3H), 0.60 (s, 6H). 13C NMR (101 MHz, CDCl3): δ
168.3, 140.1, 136.8, 134.0, 131.3, 130.0, 129.3, 128.6,
127.7, 61.1, 14.2, 0.7. HR-MS (EI): m/z = 241.0679,
calcd for C14H13O2Si ([M-Me]+): 241.0679.
A Schlenk tube was charged with NiCl2(PCy3)2 (13.8 mg,
0.020 mmol), 2-([1,1'-biphenyl]-2-yloxy)pyridine (49.4 mg,
0.20 mmol) and THF (1.52 mL). To the stirred mixture
was added PhMe2SiZnCl solution (0.48 mL, 0.46 M
solution in THF, 0.22 mmol). The resultant mixture was
stirred at 60 °C for 2 h and then cooled to room
temperature. A 20% aqueous solution of NH4Cl (10 mL)
was added. The mixture was extracted with ethyl acetate (3
× 10 mL). The combined organic phases were dried over
anhydrous Na2SO4, concentrated by rotary evaporation,
and purified by silica gel column chromatography (eluent:
petroleum ether) to give [1,1'-biphenyl]-2-yldimethyl
Isopropyl 4-(methyldiphenylsilyl)benzoate (4b): Yield:
57.5 mg (80%); colorless oil. 1H NMR (400 MHz, CDCl3):
δ 8.03 (d, J = 8.1 Hz, 2H), 7.61 (d, J = 8.2 Hz, 2H), 7.54-
7.48 (m, 4H), 7.46-7.34 (m, 6H), 5.32-5.23 (m, 1H), 1.38
(d, J = 6.2 Hz, 6H), 0.87 (s, 3H). 13C NMR (101 MHz,
CDCl3): δ 166.3, 142.4, 135.5, 135.4, 135.3, 131.8, 129.8,
128.7, 128.1, 68.5, 22.1, 3.4. HR-MS (ESI): m/z =
361.1625, calcd for C23H25O2Si ([M+H]+): 361.1618.
1
(phenyl)silane, yield: 29.1 mg (51%), colorless oil.. H
NMR (400 MHz, CDCl3): δ 7.62 (d, J = 7.2 Hz, 1H), 7.45-
7.17 (m, 11H), 7.09 (d, J = 7.2 Hz, 2H), 0.17 (s, 6H).
Synthesis of (2-methoxyphenyl)dimethyl(phenyl)silane
from 2-phenoxypyridine.
(4-Methoxyphenyl)(methyl)diphenylsilane
(4c):[12c]
1
Yield: 38.2 mg (63%); white solid. H NMR (400 MHz,
CDCl3): δ 7.59-7.53 (m, 4H), 7.48 (d, J = 8.6 Hz, 2H),
7.45-7.35 (m, 6H), 6.96 (d, J = 8.6 Hz, 2H), 3.84 (s, 3H),
0.86 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 160.8, 136.9,
136.7, 135.4, 129.4, 128.0, 126.9, 113.8, 55.1, 3.0.
Synthesis of 2-(2-methoxyphenoxy)pyridine follows a
literature procedure.[1h] 2-Phenoxypyridine (85.5 mg, 0.5
mmol), PhI(OAc)2 (322.1 mg, 1.0 mmol), Pd(OAc)2 (11.3
mg, 0.05 mmol) and methanol (4 mL) was added to a
Schlenk tube. The mixture was stirred at 90 °C for 24 h
and then cooled to room temperature. Solvent was
removed under reduced pressure. The residue was purified
by silica gel column chromatography (eluent: petroleum
ether/EtOAc = 60:1 to 15:1) to give 2-(2-methoxyphenoxy)
pyridine, yield: 37.2 mg (37%), white solid. 1H NMR (400
MHz, CDCl3): δ 8.15 (dd, J = 1.3, 4.9 Hz, 1H), 7.68-7.61
(m, 1H), 7.23-7.17 (m, 1H), 7.14 (dd, J = 1.6, 7.8 Hz, 1H),
7.04-6.96 (m, 2H), 6.96-6.89 (m, 2H), 3.76 (s, 3H). 13C
NMR (101 MHz, CDCl3): δ 163.83, 151.90, 147.65,
142.64, 139.26, 126.10, 123.21, 121.19, 118.10, 112.97,
110.76, 55.99.
[1,1'-Biphenyl]-4-yltriphenylsilane (5a):[10b] Yield: 47.8
1
mg (58%); white solid. H NMR (400 MHz, CDCl3): δ
7.72-7.58 (m, 12H), 7.51-7.32 (m, 12H). 13C NMR (101
MHz, CDCl3): δ 142.4, 141.0, 137.0, 136.6, 134.3, 133.1,
129.8, 128.9, 128.1, 127.6, 127.3, 126.7. HR-MS (ESI):
m/z = 412.1646, calcd for C30H24Si ([M]+): 412.1642.
(4-Methoxyphenyl)triphenylsilane (5b):[12b] Yield: 24.0
1
mg (33%); white solid. H NMR (400 MHz, CDCl3): δ
7.61-7.54 (m, 6H), 7.50 (d, J = 8.6 Hz, 2H), 7.46-7.34 (m,
9H), 6.94 (d, J = 8.6 Hz, 2H), 3.83 (s, 3H). 13C NMR (101
MHz, CDCl3): δ = 161.0, 138.1, 136.5, 134.7, 129.6, 128.0,
125.0, 113.8, 55.2.
A Schlenk tube was charged with NiCl2(PCy3)2 (13.8 mg,
0.020 mmol), 2-(2-methoxyphenoxy)pyridine (40.2 mg,
0.20 mmol) and THF (1.52 mL). To the stirred mixture
was added PhMe2SiZnCl solution (0.48 mL, 0.46 M
solution in THF, 0.22 mmol). The resultant mixture was
stirred at 60 °C for 2 h and then cooled to room
temperature. A 20% aqueous solution of NH4Cl (10 mL)
was added. The mixture was extracted with ethyl acetate (3
× 10 mL). The combined organic phases were dried over
anhydrous Na2SO4, concentrated by rotary evaporation,
and purified by silica gel column chromatography (eluent:
petroleum ether) to afford (2-methoxyphenyl)dimethyl
Isopropyl 4-(triphenylsilyl)benzoate (5c): Yield: 21.0 mg
1
(25%); colorless oil. H NMR (400 MHz, CDCl3): δ 8.03
(d, J = 8.1 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.61-7.52 (m,
6H), 7.50-7.34 (m, 9H), 5.31-5.22 (m, 1H), 1.37 (d, J = 6.2
Hz, 6H). 13C NMR (101 MHz, CDCl3): δ 166.3, 140.5,
136.48, 136.45, 133.6, 131.9, 130.0, 128.6, 128.1, 68.6,
22.1. HR-MS (ESI): m/z = 423.1783, calcd for C28H27O2Si
([M+H]+): 423.1775.
1
(phenyl)silane, yield: 28.1 mg (58%), colorless oil. H
NMR (400 MHz, CDCl3): δ 7.60-7.51 (m, 2H), 7.39-7.30
(m, 4H), 7.29-7.22 (m, 1H), 6.91 (t, J = 7.2 Hz, 1H), 6.83
(d, J = 8.2 Hz, 1H), 3.73 (s, 3H), 0.55 (s, 6H).
The sequential reaction
Synthesis of [1,1'-biphenyl]-2-yldimethyl(phenyl)silane
from 2-phenoxypyridine.
Acknowledgements
Synthesis of 2-([1,1'-biphenyl]-2-yloxy)pyridine follows a
literature procedure.[1b] 2-Phenoxypyridine (85.5 mg, 0.5
mmol), potassium phenyltrifluoroborates (230 mg, 1.25
mmol), Ag2CO3 (276 mg, 1.0 mmol), p-benzoquinone
(54.1 mg, 0.5 mmol), Pd(OAc)2 (11.3 mg, 0.05 mmol),
DMSO (142 μL, 2.0 mmol) H2O (72 μL, 4.0 mmol) and
CH2Cl2 (15 mL) was added to a Schlenk tube. The mixture
was stirred at 130 °C for 48 h and then cooled to room
temperature. The solution was filtered through a plug of
silica gel which was rinsed with EtOAc (20 mL). The
filtrate was concentrated and purified by silica gel column
chromatography (eluent: petroleum ether/EtOAc = 100:1
to 60:1) to give 2-([1,1'-biphenyl]-2-yloxy)pyridine, yield:
This work was supported by the National Basic Research
Program of China (Grant No. 2015CB856600).
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FULL PAPER
Nickel-Catalyzed Reaction of Aryl 2-Pyridyl
Ethers with Silylzinc Chlorides: Silylation of Aryl
2-Pyridyl Ethers via Cleavage of the Carbon
Oxygen Bond
Adv. Synth. Catal. Year, Volume, Page – Page
Ying-Ying Kong, Zhong-Xia Wang*
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