Highly Efficient Bulky α-Diimine Palladium Complexes for Suzuki-Miyaura Cross-Coupling Reaction

Article abstract of DOI:10.1002/cjoc.201600616

A series of bulky 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine methyl palladium chloride complexes (C1—C6) with different steric and electronic substituent have been applied in Suzuki-Miyaura cross-coupling reactions. The influence of these substituents was investigated by comparing the catalytic performance of the complexes in the cross-coupling reactions and it can be found that the complex with bulky and electron-donating substituent is facilitated for the cross-coupling reaction of aryl halides with arylboronic acids under ambient atmosphere. The most active complex shows a wide substrate scope in excellent yields using very low catalyst concentration of 0.01 mol%.

Full text of DOI:10.1002/cjoc.201600616

FULL PAPER
DOI: 10.1002/cjoc.201600616
Highly Efficient Bulky α-Diimine Palladium Complexes for
Suzuki-Miyaura Cross-Coupling Reaction
,a
a
,a
a,b
Ping Huo,* Jingbo Li, Wanyun Liu,* and Guangquan Mei
a
Key Laboratory of Jiangxi University for Applied Chemistry and Chemical Biology,
Yichun University, Yichun, Jiangxi 336000, China
b
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, China
A series of bulky 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine methyl palladium chloride complexes (C1
C6) with different steric and electronic substituent have been applied in Suzuki-Miyaura cross-coupling reactions.
－
The influence of these substituents was investigated by comparing the catalytic performance of the complexes in the
cross-coupling reactions and it can be found that the complex with bulky and electron-donating substituent is facili-
tated for the cross-coupling reaction of aryl halides with arylboronic acids under ambient atmosphere. The most ac-
tive complex shows a wide substrate scope in excellent yields using very low catalyst concentration of 0.01 mol%.
Keywords 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine, palladium complex, Suzuki-Miyaura reaction, aryl
halides, arylboronic acids
Introduction
complexes have been reported for use in the Suzuki-
[30-35]
Miyaura cross-coupling reaction.
Chelating NHC
The Suzuki-Miyaura cross-coupling reaction cata-
lyzed by transition metals has been one of the most
powerful and convenient tools for biaryls synthesis.
As far as we know, many different types of phosphine
ligand have been discovered for Suzuki-Miyaura
cross-coupling reaction.
palladium complexes showed excellent catalytic activi-
ties in cross-coupling reactions at elevated temperatures
[
1-9]
[
36-38]
under air.
A series of benzimidazolium- pyrazole
palladium complexes have been successfully developed
[39]
[
10,11]
by Andy Hor and his collaborators, which showed
high catalytic activity for cross-coupling of aryl halides
with arylboronic acids under homogeneous conditions.
But these ligands are often
toxic and air- and moisture-sensitive, which places sig-
nificant limits on their synthetic applications.
[
12,13]
[40]
Shiono and coworkers found that α-diimine Pd(II)
complex containing chiral sec-phenethyl groups exhib-
ited moderate activity toward the Suzuki-Miyaura
cross-coupling reactions of various aryl halides and ar-
ylboronic acids at room temperature. From above, it
could be found that a bulky and electronically rich lig-
and was beneficial for improving the catalytic activity
of palladium complex.
To search for new catalysts that exhibit high activity
and stability with a broad range of substrates in the cou-
pling reaction, we present a series of 9,10-dihydro-9,10-
ethanoanthracene-11,12-diimine methyl palladium
chloride complexes with bulky backbones and substi-
tuted aniline moieties. The bulky backbones could in-
crease the steric hindrance on the complexes, and the
different substituted aniline moieties could facilitate the
investigation of steric and electronic effects on the cata-
lytic activity.
Therefore, in the past few years, great advances have
been made in developing active and efficient catalysts
by phosphine-free ligands.
[14-21]
It is a trend that phosphine-free ligands which are
easily available, and are moisture and air stable, are in
heavy demand in the palladium-catalyzed Suzuki-
Miyaura cross-coupling reaction of aryl halides and ar-
ylboronic acids. The common used phosphine-free lig-
[22]
[23-25]
ands are heterocyclic carbenes, β-ketoamine
and
[
26]
α-diimine. When these ligands are added in the sys-
tem, the yield of product increases dramatically, indi-
cating the in-situ formation of catalyst systems. Howev-
er, it is unlikely that a quantitative in-situ complex for-
mation occurs in a short reaction time, which leads to a
waste of palladium source and ligand. In many cases, it
was found that defined palladium complexes showed a
[
27-29]
better activity than similar in-situ systems.
Recently, several air-stable phosphine-free palladium
*
E-mail: liuwanyun2006@163.com, ycxyhuoping@163.com; Tel.: 0086-0795-3201987; Fax: 0086-0795-3201987
Received September 24, 2016; accepted November 24, 2016; published online XXXX, 2017.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201600616 or from the author.
Chin. J. Chem. 2017, XX, 1—5
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1

Huo et al.
FULL PAPER
Experimental
100). Anal calcd for C35
4
H N
35 2
ClPd: C 67.20, H 5.64, N
.48; found C 67.17, H 5.69, N 4.45.
Complex C4 was obtained as a yellow crystal in
Materials and methods
1
Hexane was refluxed over metallic sodium for 24 h
before being used. Dichloromethane was dried over
88% yield. M.p. 149－150 ℃. H NMR (CDCl ) δ:
3
0.43 (s, 3H), 2.07 (s, 6H), 2.11 (s, 6H), 4.85 (s, 1H),
13
CaH for 8 h and distilled under a nitrogen atmosphere.
4.86 (s, 1H), 7.17－7.31 (m, 8H), 7.42 (s, 4H).
C
2
Other commercially available reagents were purchased
from common commercial resources and used without
further purification. The nuclear magnetic resonance
NMR (CDCl ) δ: 1.71, 18.10, 18.52, 50.33, 51.18,
3
125.81, 125.97, 126.74, 127.89, 128.35, 128.50, 128.87,
129.29, 129.52, 129.99, 136.89, 138.24, 143.43, 144.9＋6,
167.19, 172.19; EI-MS m/z (rel intensity): 755 (M ,
100). Anal. calcd for C33H N ClBr Pd: C 52.48, H 3.87,
29 2 2
N 3.71; found C 52.43, H 3.91, N 3.69.
(
NMR) was recorded on a Bruker ARX 400 NMR spec-
trometer at ambient temperature, with CDCl as the
3
1
13
solvent. Chemical shifts for the H NMR and C NMR
spectrum were given in parts per million from the peak
for internal tetramethylsilane. Elemental analysis was
done using elementar-vario EL.
Complex C5 was obtained as a yellow crystal in
1
8
0
3% yield. M.p. 178－179 ℃. H NMR (CDCl
3
) δ:
.68 (s, 3H), 5.07 (s, 1H), 5.37 (s, 1H), 6.94 (d, J＝7.0
Hz, 2H), 7.10 (d, J＝7.0 Hz, 2H), 7.28－7.36 (m, 8H),
1
3
Syntheses of (α-diimine) methyl palladium chloride
complexes (C1－C6)
7
.52 (d, J＝7.0 Hz, 2H), 7.57 (d, J＝7.0 Hz, 2H);
C
3
NMR (CDCl ) δ: 3.63, 49.68, 51.20, 123.40, 124.32,
The (α-diimine) methyl palladium chloride com-
plexes C1－C6 (Scheme 1) were synthesized according
125.58, 125.72, 129.45, 129.59, 130.10, 133.63, 133.66,
136.29, 137.20, 142.43, 143.79, 167.25, 173.77; EI-MS
[41]
＋
to the method reported, with some modifications.
A typical synthetic procedure for C1 could be de-
scribed as follows: 0.5 mmol 9,10-dihydro-9,10-etha-
noanthracene-11,12-diimine ligand and 0.5 mmol (COD)
PdMeCl were added to a Schlenk tube together with 20
mL dried dichloromethane. The reaction mixture was
then stirred for 12 h at room temperature. The solution
was filtered through Celite, and 10 mL absolute hexane
was added. The yellow complex was crystallized from
m/z (rel intensity): 610 (M , 100). Anal calcd for
C H N Cl Pd: C 57.07, H 3.47, N 4.59; found C 57.18,
29 21 2 3
H 3.51, N 4.55.
Complex C6 was obtained as a yellow crystal in
1
7
0
6% yield. M.p. 216－217 ℃. H NMR (CDCl
3
) δ:
.62 (s, 3H), 5.07 (s, 1H), 5.30 (s, 1H), 7.12 (d, J＝5.0
Hz, 2H), 7.24 (d, J＝5.0 Hz, 2H), 7.29－7.47 (m, 8H),
1
3
7
.82 (d, J＝5.5 Hz, 2H), 7.86 (d, J＝5.5 Hz, 2H);
C
3
NMR (CDCl ) δ: 3.63, 49.89, 51.26, 60.33, 122.55,
1
23.12, 125.73, 126.52, 127.27, 129.70, 135.99, 136.8＋8,
167.49, 172.42. EI-MS m/z (rel intensity): 677 (M ,
00). Anal calcd for C31 ClPd: C 54.97, H 3.12,
the mixture of dichloromethane and hexane in 82%
1
yield. M.p. 167－168 ℃. H NMR (CDCl ) δ: 0.43 (s,
3
1
21 2 6
H N F
3
7
1
1
1
H), 2.05 (s, 6H), 2.07 (s, 6H), 4.80 (s, 1H), 4.81 (s, 1H),
1
3
N 4.14; found C 55.12, H 3.08, N 4.18.
.16－7.27 (m, 14H); C NMR (CDCl ) δ: 1.11, 17.90,
3
8.32, 50.31, 51.15, 125.77, 125.93, 126.68, 127.49,
28.15, 128.30, 128.60, 129.09, 129.22, 129.39, 136.49,
Scheme 1 The (α-diimine) methyl palladium chloride com-
plexes
37.24, 142.43, 142.96, 167.19, 172.19; EI-MS m/z (rel
＋
intensity): 597 (M , 100). Anal. calcd for C H N ClPd:
33
31
2
C 66.34, H 5.23, N 4.69; found C 66.21, H 5.32, N 4.67.
Complex C2 was obtained as yellow power in 89%
1
yield. M.p. 151－152 ℃. H NMR (CDCl
3
) δ: 0.52 (s,
3
H), 1.12－1.16 (d, J＝6.2 Hz, 12H), 1.38－1.47 (d,
J＝6.2 Hz, 12H), 2.79 (m, 4H), 4.90 (s, 1H), 4.95 (s,
1
3
1
2
5
1
1
1
3
3
H), 7.24－7.30 (m, 14H); C NMR (CDCl ) δ: 3.95,
3.28, 23.39, 23.88, 24.31, 28.66, 29.07, 29.45, 50.48,
1.35, 123.43, 124.10, 126.22, 126.26, 127.55, 128.28,
28.49, 128.66, 137.23, 137.97, 139.35, 140.00, 140.3＋9,
67.03, 171.89; EI-MS m/z (rel intensity): 710 (M ,
00). Anal. calcd for C41H N ClPd: C 69.39, H 6.68, N
47 2
.95; found C 69.33, H 6.72, N 3.92.
General procedure for Suzuki-Miyaura reaction
A 50 mL flask was charged with arylboronic acid
(1.2 mmol), the appropriate amount of palladium com-
Complex C3 was obtained as a yellow crystal in
1
8
0
2
7
1
1
1
1
8% yield. M.p. 177－178 ℃. H NMR (CDCl
3
) δ:
plex, base (2.0 mmol), EtOH/H O (V/V, 1∶1, 4 mL)
2
.43 (s, 3H), 1.99 (s, 6H), 2.02 (s, 6H), 2.35 (s, 3H),
.38 (s, 3H), 4.83 (s, 1H), 4.84 (s, 1H), 6.96 (s, 2H),
.02 (s, 2H), 7.24－7.27 (m, 8H); C NMR (CDCl ) δ:
3
.18, 17.84, 18.26, 21.20, 21.28, 31.63, 50.28, 51.14,
25.75, 125.91, 128.03, 128.92, 128.98, 129.12, 129.14,
29.23, 135.94, 136.68, 137.02, 137.43, 140.00, 140.5＋8,
67.40, 172.37; EI-MS m/z (rel intensity): 625 (M ,
and aryl halide (1.0 mmol) were added. The reaction
was stirred at room temperature or 78 ℃ for the certain
time. The progress of the reaction was monitored by
TLC. After completion of the reaction, it was extracted
with ether (10 mL×3) and washed with water. The
combined ether extract was dried over anhydrous
Na SO . The filtrate was concentrated under reduced
1
3
2
4
2
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Chin. J. Chem. 2017, XX, 1—5

Palladium Complexes for Suzuki-Miyaura Cross-Coupling Reaction
pressure. The crude material was purified by column
chromatography over silica gel using hexane/ethyl ace-
tate (V/V, 9∶1) to get the desired coupling product. The
purified products were characterized by comparing their
conditions, precatalyst C3 allows for excellent yields
with the inexpensive and environmentally friendly sol-
2 3 4
vent EtOH/H O (V/V, 1∶1) and base K PO .
1
13
Activity differences of complexes C1－C6
H and C NMR spectra with those found in the litera-
tures.
To examine the effect of the catalysts on the Suzuki
reaction, the cross-coupling reaction of 4-bromoaceto-
phenone and phenylboronic acid was chosen as a model
Results and Discussion
reaction. The reaction was conducted with K
base at room temperature for 2 h in ethanol/water (V/V,
∶1). The results are summarized in Table 2.
3 4
PO as
Catalytic studies
1
To investigate the catalytic activity of the (α-diimine)
methyl palladium chloride complexes, we evaluated the
reaction conditions for the Suzuki-Miyaura cross-cou-
pling reaction using the reaction of 4-bromoacetophe-
none with phenylboronic acid with 0.01 mol% of com-
plex C3 within a reaction time 2 h (Table 1). Initially,
Table 2 Influence of α-diimine Pd(II) complexes on the cross-
coupling reaction of 4-bromoacetophenone with phenylboronic
a
acid
b
c
Entry
Catalyst
Pd(OAc)
C1
Yield /%
TON
2600
9200
9500
9900
8600
6200
5500
3 4
we ran the reaction in air with K PO in different sol-
1
2
3
4
5
6
2
26
92
95
99
86
62
55
vents (Entries 1－8, Table 1) and found that the polarity
of the solvent had a profound effect on the yield. For
example, the polar solvents such as ethanol (EtOH),
tetrahydrofuran (THF), isopropanol (i-PrOH), N,N-di-
methylformamide (DMF) provided the product in mod-
erate yield (Entries 1－4, Table 1), whereas when the
nonpolar solvent toluene (Entry 5, Table 1) was used,
the poor yield could be observed. Meanwhile, using
organic/water cosolvents, the reaction activities were
dramatically improved (Entries 6－8, Table 1). Among
C2
C3
C4
C5
7
C6
a
Reaction conditions: 1.0 mmol of 4-bromoacetophenone, 1.2
mmol of phenylboronic acid, 2.0 mmol of K PO , 0.01 mol%
3
4
the tested organic/water cosolvents, the EtOH/H
∶1) system could afford the highest yield (Entry 6,
Table 1). While varying the base (Entries 6, 9－13, Ta-
ble 1), we found that the K PO was superior, leading to
high yields within 2 h. The other bases such as KOH,
KOt-Bu, Na CO , K CO and Cs CO gave slightly
2
O (V/V,
catalyst, 4 mL EtOH/H O (V/V, 1∶1), room temperature, 2 h.
2
1
b
c
Isolated yields. TON＝mol of product per mol of catalyst.
3
4
Table 2 revealed that the α-diimine Pd(II) complexes
were effective as catalysts for Suzuki cross-coupling.
For comparison, the cross-coupling reaction of
2
3
2
3
2
3
lower yields. Therefore, even under mild reaction
4
-bromoacetophenone and phenylboronic acid was also
performed with Pd(OAc) and complexes C1－C6 un-
der the established conditions. In the absence of ligands,
only 26% yield of product was produced in the presence
2
Table 1 Optimization of reaction conditions at room tempera-
ture
a
b
Entry Solvent
Base
Yield /%
86
of 0.01 mol% Pd(OAc)
the presence of the α-diimine palladium complexes C1
C6, the yield of product and TON increased dramati-
2
(Entry 1, Table 2). However, in
1
2
3
4
5
6
7
8
9
EtOH
THF
K
3
3
PO
4
4
4
4
4
4
4
4
－
K
PO
77
cally, to a range of 55%－99% and 5500－9900 (En-
tries 2－7, Table 2). It could be explained by that the
reactivity and stability of the metal catalysts were in-
i-PrOH
DMF
K PO
3
81
K PO
3
84
creased by use of increasing efficacious supporting lig-
Toluene
K PO
3
42
[42]
ands.
Among the (α-diimine) methyl palladium
EtOH/H O (V/V, 1∶1)
3
K PO
99
2
chloride complexes C1－C6 investigated, the highest
yield was obtained by C3 with 2,4,6-trimethyl groups
on the aniline moiety (Entry 4, Table 2). In this case, the
conversion of the product reached 99%. Meanwhile, C2
with 2,6-diisopropyl groups on the aniline moiety also
could obtain high conversion (Entry 3, Table 2). These
phenomena were due to the steric hindrance effect,
which was beneficial to the catalysis of the coupling
EtOH/H O (V/V, 2∶1)
3
K PO
93
2
EtOH/H O (V/V, 1∶2)
3
K PO
91
2
EtOH/H O (V/V, 1∶1)
KOH
88
2
1
0
EtOH/H O (V/V, 1∶1)
KOt-Bu
Na CO
K CO
87
2
1
1
2
3
EtOH/H O (V/V, 1∶1)
2
3
90
2
1
1
EtOH/H O (V/V, 1∶1)
92
[43]
2
2
3
reactions. In addition to the steric hindrance effect,
EtOH/H O (V/V, 1∶1)
Cs CO
2
3
95
2
the electron effect also had a great influence on the cou-
pling reaction. C6 with a strong electron-withdrawing
trifluoromethyl group on the para position of the aniline
(Entry 7, Table 2), exhibited the worst activity under the
a
Reaction conditions: 1.0 mmol of 4-bromoacetophenone, 1.2
mmol of phenylboronic acid, 2.0 mmol of base, 0.01 mol% com-
b
plex C3, 4 mL solvent, 2 h. Isolated yields.
Chin. J. Chem. 2017, XX, 1—5
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3

Huo et al.
FULL PAPER
same conditions (55% yield). These results could be
ascribed to the increase in steric hindrance and elec-
tron-donating ability of the aniline moieties of the lig-
and, leading to an increase in the rate of oxidative addi-
tion and the stabilization of the palladium species.
Continued
b
Entry
4
Aryl halide
Aryl boronic
Time/hYield /%
2
2
2
98
98
99
Substrate scope
5
6
As demonstrated before, the catalyst precursor C3
was highly active even at low catalyst concentrations.
Therefore, with optimal reaction conditions in hand, we
tested the scope of precatalyst C3 in the Suzuki-
Miyaura cross-coupling reaction using different para-,
meta- and ortho-substituted aryl chlorides and boronic
acids at low catalyst concentrations (Table 3). Unsur-
prisingly, compared with the yield of the cross-coupling
reaction catalyzed by corresponding α-diimine ligand
CH3
Br
7
8
3
3
87
92
[
21]
and Pd(OAc)
2
,
the α-diimine palladium complex re-
quired a lower catalyst amount to obtain a high yield.
Overall, aryl bromides were better substrates than an
aryl chloride (Entries 17 and 18, Table 3) and an elec-
tron-rich or electron-deficient group at the para-position
of aryl bromides could obtain high yielding (Entries 1－
9
4
80
6
, Table 3). In contrast, reaction with the same group at
the more hindered ortho-position leads to a significantly
lower yield (Entries 7 and 9, Table 3). Most remarkably,
aryl bromides bearing a naphthalene ring underwent
reaction smoothly with yield as high as 92% within 3 h
1
0
1
2
2
2
2
2
96
99
95
93
91
1
(
Entry 8, Table 3). In this study, the effect of various
para-substituents on the arylboronic acids toward the
cross coupling was investigated (Entries 10－14, Table
12
3
). It could be found that no significant difference was
observed in yield or in the reaction time. When the
phenylboronic with ortho-substituents reacted with the
aryl halide, the catalytic system could show good activ-
ity through prolonged reaction time (Entry 15, Table 3).
We extended the substrate scope to 1-naphthylboronic
acid, it could be found high yield in 3 h (Entry 16, Table
1
3
4
1
CH3
3
). 4-Chloroacetophenone was coupled with 0.20 mol%
1
5
6
3
84
of C3 in 76% yield with 10 h (Entry 17, Table 3),
whereas when the more challenging 4-chlorotoluene
was used, a lower yield was obtained (Entry 18, Table
B(OH)2
1
3
88
76
35
3
).
Table 3 Suzuki cross-coupling reaction of aryl halides with
c
1
7
8
10
10
a
phenylboronic acid under aerobic conditions
c
1
a
Reaction conditions: 1.0 mmol of aryl bromide, 1.2 mmol of
arylboronic acid, 2.0 mmol of K PO , 0.01 mol% α-diimine Pd(II)
b
3
4
Entry
1
Aryl halide
Aryl boronic Time/h Yield /%
complex C3, 4 mL EtOH/H O (V/V, 1∶1), room temperature.
2
b
c
Isolated yields. Reaction conditions: 1.0 mmol of aryl chloride,
2
2
2
96
94
99
1
.2 mmol of aryl boronic acid, 2.0 mmol of K PO , 0.20 mol%
3
4
α-diimine Pd(II) complex C3, 4 mL EtOH/H O (V/V, 1∶1), reac-
2
2
3
tion temperature: 78 ℃.
Conclusions
An easy-to-handle catalytic system was reported for
4
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Chin. J. Chem. 2017, XX, 1—5

Palladium Complexes for Suzuki-Miyaura Cross-Coupling Reaction
the Suzuki-Miyaura coupling reaction using three-di-
mensional geometry (α-diimine) methyl palladium
chloride complexes C1－C6 as catalysts. The catalytic
system provided a mild and aerial condition for the cou-
pling reaction of aryl bromides with arylboronic acid. A
wide range of substrates could be coupled with aryl-
boronic acids to afford the desired products in good to
excellent yields. Furthermore, the catalytic system also
gave excellent yields toward several chlorides. The cat-
alytic reaction results demonstrated that the complex C3
with 2,4,6-trimethyl groups on the aniline moiety was a
highly efficient catalyst in Suzuki-Miyaura cross-cou-
pling reaction.
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This work was supported by the National Natural
Science Foundation of China (No. 21664014), the Nat-
ural Science Foundation of Jiangxi Province (No.
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