A Palladium Bipyridyl Complex Grafted onto Nanosized MCM-41 as a Heterogeneous Catalyst for Negishi Coupling

Article abstract of DOI:10.1002/cctc.201200388

The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70°C for electron-deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110°C were required if electron-rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50°C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.

Full text of DOI:10.1002/cctc.201200388

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DOI: 10.1002/cctc.201200388
A Palladium Bipyridyl Complex Grafted onto Nanosized
MCM-41 as a Heterogeneous Catalyst for Negishi Coupling
Wei-Yi Wu,[a] Tze-Chiao Lin,[a] Tamotsu Takahashi,[b] Fu-Yu Tsai,*[a] and Chung-Yuan Mou*[c]
The Negishi coupling of aryl bromides or acyl chlorides with
organozinc chlorides catalyzed by a palladium bipyridyl com-
plex anchored on nanosized mobile crystalline material 41
(MCM-41) were investigated. The reactions proceeded smooth-
ly with a very low catalyst loading in THF at 708C for electron-
deficient aryl bromides, which gave good to high yields of the
Negishi coupling products. However, reactions in toluene at
110 8C were required if electron-rich aryl bromides were em-
ployed. For acyl chlorides, the reactions could be performed in
THF at 508C and the corresponding ketones and ynones were
obtained in high yields. After centrifugation, it was possible to
easily recover the supported catalyst from the reaction mix-
ture, and this could be reused several times without any re-
treatment or regeneration with only a slight decrease in
activity.
Introduction
The palladium-catalyzed cross-coupling of aryl or vinyl halides
with organozinc reagents, known as the Negishi coupling, is
one of the most powerful methods for the straightforward
construction of carbon–carbon bonds in synthetic chemistry.[1,2]
At present, the Negishi reaction is an indispensable palladium-
catalyzed cross-coupling reaction; it has applications in all
areas of organic chemistry, for example, in the preparation of
biologically-active molecules,[3] ligands,[4] polymers,[5] and vari-
ous materials.[6] The Negishi coupling is generally performed in
a homogeneous phase with high loadings of catalyst (ꢀ5%),
which makes separation of the expensive palladium catalyst
from the products and recovery from the reaction solution dif-
ficult. Therefore, it is desirable to have a catalytic system in
which the loadings of the catalytic complex can be reduced
and separation and recovery are easy. The reaction becomes
highly valuable with regards to various economic and environ-
mental concerns, if it is adapted to heterogeneous conditions
to enable recycling. Palladium on carbon associated with
AsPh3 and palladium nanoparticles has been reported as a het-
erogeneous catalyst for the Negishi coupling of aryl iodides
and organozinc reagents; however, high catalyst loadings (10
and 0.5 mol%) are still required, and no recycling or reuse
studies have been performed.[7,8]
On the other hand, synthesis of metal complex-supported
catalysts based on the heterogenization of successful homoge-
neous catalysts is of current interest. Ordered mesoporous
silica (OMS) materials with tunable and uniform pore diameters
(2–30 nm), high surface areas (>600 m2 gÀ1), high thermal sta-
bilities, and large amounts of silanol groups for functionaliza-
tion are some of the best candidates as solid supports for im-
mobilizing transition-metal complexes. These heterogenized
catalysts may be easily separated from the reaction mixture
and recycled.[9] Recently, there has been a rapid increase in the
use of palladium immobilized mesoporous silica as a recyclable
catalyst for carbon–carbon bond forming reactions, such as
the Mizoroki–Heck reaction,[10] Suzuki–Miyaura reaction,[11] So-
nogashi–Hagihara reaction,[12] Migita–Kosugi–Stille reaction,[13]
and Kumada–Tamao–Corriu reaction.[14] In spite of the diverse
range of applications of palladium immobilized mesoporous
silica catalysts in the aforementioned reactions, there have, to
date, been no reports of the immobilization of palladium com-
plexes on OMS supports for use in the Negishi coupling. The
difficulty is probably associated with the moisture sensitive
nature of organozinc derivatives.
We report here on the synthesis of a nanosized mobile crys-
talline material 41(MCM-41) supported palladium bipyridyl
complex (denoted NS-MCM-41-Pd, Figure 1), which is an excel-
lent heterogeneous catalyst for carbon–carbon bond forming
reactions. We used metal complexes with ligands that con-
tained trialkoxysilane terminal groups; this allowed for facile
homogeneous incorporation of metal complexes that were co-
valently bound to the porous support.[10h,12c,14–15] The funda-
mental advantage of this catalyst is its short and highly-con-
nected wormhole-like channels, which allow for easy exchange
of reactants and products throughout the nanochannels. This
avoids the saturation phenomenon that occurs if a very low
[a] Dr. W.-Y. Wu, T.-C. Lin, Prof. F.-Y. Tsai
Institute of Organic and Polymeric Materials
National Taipei University of Technology, Taipei 106 (Taiwan)
E-mail: fuyutsai@ntut.edu.tw
[b] Prof. T. Takahashi
Catalysis Research Center and Graduate School of Life Science
Hokkaido University, Sapporo, Hokkaido (Japan)
[c] Prof. C.-Y. Mou
Department of Chemistry
National Taiwan University
Taipei 106 (Taiwan)
E-mail: cymou@ntu.edu.tw
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201200388.
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in THF with 0.1 mol% NS-MCM-41-Pd in the presence of
0.2 mol% PPh3 at 708C, giving 3aa in a 99% isolated yield
within 3 h (Table 1, Entry 1). It is notable that attempts to
lower the reaction temperature to room temperature and
508C afforded no product and only 37% yield of 3aa,
respectively.
We previously found that addition of PPh3 for NS-MCM-41-
Pd-catalyzed carbon–carbon bond forming reactions is critical
to stabilize the Pd0 species before it undergoes oxidative addi-
tion with aryl halides.[12c,14–15] Hence, no desired Negishi cou-
pling products were observed in the absence of PPh3 (Entry 2).
To our delight, an excellent activity was observed if the catalyst
loading was further reduced to 0.01 mol% and the amount of
1a was increased to 28 mmol. 3aa was isolated in an 89%
Figure 1. Covalent loading of the catalytic complex in nanosized
MCM-41-Pd.
catalyst loading is used.[10m]
A
second advantage of the catalyst
is that it preserved the integrity
of the metal complexes in the
silica mesopores. The nanocon-
finement effect results in
a higher catalytic efficiency. In
this report, we present the Ne-
gishi coupling of aryl bromides
or acyl chlorides with organozinc
chlorides by using a very low
NS-MCM-41-Pd loading, which
provides an efficient and recycla-
ble catalytic system, and thus
renders the Negishi coupling
a more “green” process.
Table 1. Nanosized MCM-41-Pd-catalyzed Negishi coupling of aryl bromides with phenylzinc chloride.[a]
Entry
1
Aryl bromide
[Pd]
[mol%]
t
[h]
Product
Yield
[%][b]
TON
990
0.1
3
99
1a
1a
1a
3aa
3aa
3aa
2[c]
3[d]
0.1
0.01
3
24
0
89
0
8900
4
0.1
3
48
24
99
61
88
990
6100
880
1b
1c
1d
3ba
3ca
3da
5[d]
0.01
0.1
6
Results and Discussion
NS-MCM-41-Pd was prepared ac-
cording to our previously de-
scribed procedures.[10h,14] After
grafting of the palladium bipyr-
idyl complex onto NS-MCM-41
walls, the surface area, pore
volume, and pore diameter de-
7
8
0.1
0.1
24
24
94
80
940
800
1e
3ea
creased
from
880 m2 gÀ1
,
1.23 cm3 gÀ1, and 2.9 nm to
660 m2 gÀ1, 0.88 cm3 gÀ1, and
2.6 nm, respectively. The amount
of palladium complex anchored
on the MCM-41 walls was esti-
mated to be 0.14 mmolgÀ1 by
inductively coupled plasma mass
spectrometry (ICP-MASS) analy-
sis. The results of NS-MCM-41-
Pd-catalyzed Negishi coupling of
various aryl bromides, 1, with
phenylzinc chloride, 2a, are
shown in Table 1. The coupling
of 1a (2.8 mmol) with 2a
(5.6 mmol) proceeded smoothly
1 f
3 fa
9
0.1
0.1
6
93
92
930
920
1g
3ga
10
24
1h
1i
3ha
3ia
3ja
11[e]
0.1
24
24
42
99
420
12[d,f]
0.01
9900
1j
[a] Reaction conditions: 1 (2.8 mmol), 2a (5.6 mmol), NS-MCM-41-Pd (20 mg), [PPh3]:[Pd]=2:1, THF, 708C.
[b] Isolated yields. [c] In the absence of PPh3. [d] 28 mmol of 1 and 56 mmol of 2a were used. [e] Toluene was
used as the solvent at 1108C. [f] At room temperature in the absence of PPh3.
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yield, which corresponds to a turnover number (TON) of 8900
(Entry 3); this is comparable to the reported efficiency of ho-
mogeneous catalysis for the coupling of aryl bromides and or-
ganozinc reagents under a low catalyst loading.[2c,h,j] As illus-
trated in Entries 4–10, electron-deficient, ring-fused, and heter-
oaryl bromides, such as 1b–d, 1e–f, and 1g–h, also underwent
Negishi coupling very efficiently, which led to the formation of
their corresponding products in excellent yields under catalyst
loadings of between 0.01–0.1 mol%. It is also notable that aryl
chlorides could not couple with organozinc reagents under
the reaction conditions (Entry 6), hence the CÀCl bond remains
intact. For electron-rich aryl bromide 1i, the reaction did not
proceed under the aforementioned conditions. The use of tolu-
ene instead of THF as a solvent to elevate the reaction temper-
ature to 1108C gave 3ia in
loading range to deliver the corresponding products in yields
between 64 and 97% (Entries 1–7). If 2-bromonaphthalene, 1e,
and 9-bromoanthrathene, 1 f, were catalyzed by 0.1 mol% NS-
MCM-41-Pd, 5ea–5 fc were formed in high yields (Entries 8–
11).
Cross-coupling of aryl bromides and alkynylzinc chlorides
was found to be much less reactive than that of aryl- and alkyl-
zinc chlorides. This phenomenon is also observed in homoge-
neous catalysis[2k] and palladium nanoparticle-catalyzed Negishi
coupling.[8] Therefore, performance of the reaction at a higher
catalyst loading level is required (Table 4). The reaction of elec-
tron-deficient aryl bromides with alkynylzinc chlorides by using
1 mol% NS-MCM-41-Pd as the catalyst resulted in the forma-
tion of the desired internal alkynes in good to high yields in
a 42% yield in 24 h (Entry 11).
This result indicates that the oxi-
dative addition of aryl bromide
Table 2. Nanosized MCM-41-Pd-catalyzed Negishi coupling of aryl bromides with arylzinc chloride.[a]
to palladium is probably the
rate-determining step. Our cata-
lytic system can also be success-
fully applied to benzyl bromide,
1j, in this way; the TON for the
formation of 3ja can reach 9900
at room temperature without
the addition of PPh3 (Entry 12).
If a range of arylzinc chlorides
were utilized as the nucleo-
philes, the coupling of electron-
deficient aryl bromides with 2b-
c took place smoothly in excel-
lent yields under very low cata-
lyst loadings (Table 2, Entries 1–
2, 4–5, and 7–8). However, if
Entry Aryl bromide
Arylzinc chloride
[Pd]
[mol%] [h]
t
Product
Yield TON
[%][b]
1[c]
0.01
0.01
24
24
99
99
9900
9900
1a
2b
2c
3ab
3ac
2[c]
1a
3
1a
0.1
48
66
660
2d
2b
3ad
3cb
4[c]
0.01
0.01
48
48
63
68
6300
6800
1c
1c
sterically-hindered
o-tolylzinc
5[c]
2c
chloride was coupled with aryl
bromides, it only resulted in the
formation of cross-coupled prod-
ucts with yields between 48 and
66% (Entries 3, 6, and 9). Elec-
tron-rich or sterically-hindered
aryl bromides, 1i and 1k, in tol-
uene at 1108C with 0.2 mol%
NS-MCM-41-Pd as the catalyst,
gave 3ic and 3kb in 76 and
25% yields, respectively (En-
tries 10 and 11).
3cc
6
1c
2d
0.1
48
62
620
3cd
3db
7
8
2b
2c
0.1
0.1
24
24
94
93
940
930
1d
1d
3dc
9
1d
2d
2c
0.1
0.2
96
24
48
76
480
380
The utility of this reaction pro-
tocol for alkylzinc chlorides was
also evaluated (Table 3). The cou-
pling of aryl bromides with alkly-
zinc chlorides proceeded at
a slightly slower rate compared
with the analogous coupling of
arylzinc chlorides. Therefore, 1a
and 1c–d reacted with 4a–
c under a 0.02–0.1 mol% catalyst
3dd
3ic
10[d]
1i
11[d]
2b
0.2
48
25
150
1k
3kb
[a] Reaction conditions: 1 (2.8 mmol), 2 (5.6 mmol), NS-MCM-41-Pd (20 mg), [PPh3]:[Pd]=2:1, THF, 708C. [b] Iso-
lated yields. [c] 28 mmol of 1 and 56 mmol of 2 were used. [d] Toluene was used as the solvent at 1108C.
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nied by 95 and 96% yields of
diaryl ketones in only 12 h (En-
tries 2 and 3). A variety of acyl
chlorides could also couple with
arylzinc chlorides in reaction
times of 3–6 h by using
0.1 mol% NS-MCM-41-Pd; this
gave the corresponding diaryl
ketones in high yields (Entries 4–
7 and 10–11). Even if the sterical-
ly-hindered o-toluoyl chloride,
8d, was employed, 87 and 89%
yields of 9da and 9 db could be
obtained, respectively (Entries 8
and 9). 2-furoyl chloride, 8 f, and
Table 3. Nanosized MCM-41-Pd-catalyzed Negishi coupling of aryl bromides with alkylzinc chloride.[a]
Entry
1
Aryl bromide
Alkylzinc chloride
[Pd]
[mol%]
t
[h]
Product
Yield
[%][b]
TON
820
CH3ZnCl
4a
0.1
3
82
76
1a
1a
5aa
5ab
n-C4H9ZnCl
4b
2[c]
0.02
24
3800
C6H5CH2ZnCl
4c
3
1a
0.1
3
94
940
5ac
5ca
5cb
4
4a
4b
0.1
3
77
64
770
2-thiophenecarbonyl
chloride,
1c
1c
8g, were also found to couple
with 2a very efficiently to afford
excellent yields of the Negishi
coupling products (Entries 12
and 13).
5[c]
0.02
48
3200
6
7
1c
4c
4a
0.1
0.1
6
97
95
970
950
5cc
Acyl chlorides also coupled
with alkyl- and alkynylzinc chlor-
ides, and the results are sum-
marized in Table 6. In the case of
4b, not only aroyl but also het-
eroaroyl chlorides could be ap-
plied to give the desired cross-
coupled products in yields be-
tween 47 and 85% in the pres-
ence of 0.1 mol% NS-MCM-41-
Pd (Entries 1–6). After successful
application of the reactions with
alkylzinc chlorides, we investigat-
ed the efficiency of the coupling
of alkynylzinc chlorides with acyl
chlorides. As shown in Entries 7–
11 of Table 6, acyl chlorides cou-
pled with 6a more effectively
than aryl bromides. Good yields
of ynones were obtained at a cat-
alyst level of only 0.1 mol% in
6 h.
12
1d
5da
8
4a
4c
4a
0.1
0.1
0.1
12
12
24
92
99
96
920
990
960
1e
1e
5ea
5ec
5 fa
9
10
1 f
1 f
11
4c
0.1
24
99
990
5 fc
[a] Reaction conditions: 1 (2.8 mmol), 4 (5.6 mmol), NS-MCM-41-Pd (20 mg), [PPh3]:[Pd]=2:1, THF, 708C. [b] Iso-
lated yields. [c] 14 mmol of 1 and 28 mmol of 4 were used.
One of the purposes of de-
signing this heterogeneous cata-
24 h (Entries 1–7). Satisfactory results could also be achieved
for the coupling of bromobenzene, 1l, and alkynylzinc chlor-
ides in toluene at 1108C (Entries 8–10).
lyst is to enable catalytic recycling in subsequent reactions;
this is desirable from the viewpoint of economic and environ-
mental sustainability. The results with recycled NS-MCM-41-Pd
are shown in Table 7. All recycling reactions were performed
by using 0.1 mol% of catalyst, with the exception of Entry 3.
After the reactions had been conducted under the conditions
shown in Table 7, the reaction mixture from the first run was
centrifuged and the obtained solid was washed alternately
with 3n HCl aqueous solution and THF twice, and then dried
in a vacuum overnight. The recovered catalyst was then
reused without any retreatment or regeneration for the next
run in the same reaction under identical conditions. All reac-
We then examined the coupling of acyl chlorides, 8, with ar-
ylzinc chlorides (Table 5). The oxidative addition of acyl chlo-
ride to palladium was faster than that of aryl bromide. The
cross-coupling reaction could take place at 508C in the ab-
sence of PPh3, and an 85% yield of 9aa was obtained after
24 h in the presence of 0.1 mol% NS-MCM-41-Pd (Entry 1).
However, in the presence of PPh3 at a catalyst loading level of
0.01 mol%, 8a coupled with 2a, and 2b much more efficiently,
rendering TON values of 9500 and 9600 that were accompa-
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an increased reaction rate, the
so-called “confinement effect”,
which owes to activated states
that have a longer lifetime in
a confined space.[16,17] Thirdly, it
is likely that nanosized MCM-41
could be suspended in other sol-
vents, such as water, which
makes future developments of
catalytic organic reactions in
aqueous media more feasible.[18]
Table 4. Nanosized MCM-41-Pd-catalyzed Negishi coupling of aryl bromides with alkynylzinc chloride.[a]
Entry
1
Aryl bromide
Alkynylzinc chloride
Product
Yield
[%][b]
TON
99
99
86
96
78
72
92
55
64
68
76
1a
1a
6a
6b
7aa
7ab
7ac
7ca
7cb
7cc
7da
7la
2
86
3
1a
96
Conclusions
6c
6a
4
78
We have proved that NS-MCM-
41-Pd is a highly efficient and re-
cyclable heterogeneous catalyst
for the coupling of a wide range
of aryl bromides and acyl chlor-
ides with organozinc chlorides.
This method can be performed
on a large scale (up to 28 mmol)
with a very low catalyst loading
(0.01 mol%), which renders it
suitable for practical synthetic
applications. Furthermore, the
NS-MCM-41-Pd catalyst also ex-
hibited excellent recyclability
and stability if a catalyst loading
of only 0.1 mol% was used for
the recycling studies. The results
of this study demonstrate the
usefulness of a grafted palladi-
um bipyridyl complex on nano-
sized mesoporous silica as a het-
1c
1c
5
6b
6c
6a
6a
6b
6c
72
6
1c
92
7
55
1d
8[c]
9[c]
10[c]
64
1l
1l
68
7lb
7lc
1l
760
[a] Reaction conditions: 1 (1.4 mmol), 2a (2.8 mmol), NS-MCM-41-Pd (100 mg, 1 mol%), PPh3 (2 mol%), THF,
708C for 24 h. [b] Isolated yields. [c] Toluene was used as the solvent at 1108C.
tions showed only a slight decrease in the activity of NS-MCM-
erogeneous catalyst for a wide range of Negishi coupling.
41-Pd, which indicates its high stability upon workup and ex-
cellent recyclability for the Negishi coupling. Another prelimi-
nary experiment was performed to determine the leaching of Experimental Section
dissolved palladium species in solution. After the initial run of
All reactions involving air- and moisture-sensitive conditions were
Entry 1 in Table 1, the reaction solution was filtered through
a dry Celite pad under nitrogen to remove NS-MCM-41-Pd and
any insoluble species. The palladium content in the filtrate was
then analyzed by ICP-MASS, and only 2.1 ppm of palladium
was found in the solution, which indicated that the catalytic
activity may mainly result from the grafted palladium complex.
Finally, we would like to comment on some of the general
features in our NS-MCM-41-Pd catalyst. There are several ad-
vantages in the material’s design for catalysis. First, the cova-
lent attachment of the metal complex reduces leaching and in-
creases reusability.[11b] Secondly, often the diffusional problems
associated with heterogenization in solid supports, whereas
the use of nanosized complex-silica materials yields high levels
of conversion without transport limitation. The nanosize of the
support makes diffusion between catalytic sites and the exter-
nal solution more facile, the limited nanospace of the internal
pores makes repeated collisions dominate. This often leads to
performed under a dry nitrogen atmosphere. THF and toluene
were distilled from sodium benzophenone ketyl and stored under
a dry nitrogen atmosphere. Chemicals were purchased from Al-
drich, Merck, or ARCOS Co. Ltd. and were used without further pu-
rification. 4,4’-Bis(bromomethyl)-2,2’-bipyridine,[19] nanosized MCM-
41,[20] and NS-MCM-41-Pd[10h,14] were prepared according to the
previously published procedures. The palladium content was deter-
mined by ICP-MASS analysis with a Perkin–Elmer Elan-6000 instru-
ment. The melting points of solid Negishi coupling products were
1
recorded on a melting point apparatus and were uncorrected. H-
and 13C NMR spectra were recorded in CDCl3 solution at 258C on
a Varian 200 NMR spectrometer.
Preparation of aryl-, alkyl-, and alkynylzinc chlorides
The corresponding organomagnesium in THF or organolithium in
THF or hexane (5.6 mmol) were added to an anhydrous ZnCl2 THF
solution (5.6 mmol in 5 mL THF) at 08C, and the resulting solution
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was stirred at room temperature
for 1 h. The solution of the organo-
zinc derivative was then used di-
rectly without purification.
Table 5. Nanosized MCM-41-Pd-catalyzed Negishi coupling of acyl chlorides with arylzinc chloride.[a]
Entry
1[c]
Acyl chloride
Arylzinc chloride
[Pd]
[mol%]
t
[h]
Product
Yield
[%][b]
TON
850
General procedure for the NS-
MCM-41-Pd-catalyzed Negishi
coupling
0.1
24
85
Under a nitrogen atmosphere, the
freshly-prepared organozinc solu-
tion was transferred into a mixture
8a
8a
2a
2a
9aa
9aa
2[d]
3[d]
0.01
0.01
12
12
95
96
9500
9600
of
NS-MCM-41-Pd
PPh3
(20 mg,
(1.5 mg,
8a
2.8 mmol-Pd),
5.6 mmol), and aryl bromide or acyl
chloride (2.8 mmol) in 5 mL of THF.
(In the case of 0.01 mol% catalyst
loading, 28 mmol of aryl bromide
or acyl chloride were used. For the
reactions shown in Table 4, 100 mg
of NS-MCM-41-Pd and 1.4 mmol of
aryl bromide were used.). The reac-
tion mixture was stirred at 708C or
508C (the reaction temperature
was 1108C if toluene was em-
ployed as the solvent). After cool-
ing the reaction to room tempera-
ture, the reaction mixture was
quenched with 3n HCl aqueous
solution and extracted with EtOAc;
the combined organic phase was
dried over MgSO4, and the solvent
was then removed under vacuum.
Column chromatography on silica
gel afforded the desired product.
All known Negishi coupling prod-
ucts obtained were pure, and their
spectra data (1H, and 13C NMR) and
melting points were in agreement
with authentic samples (see Sup-
porting Information).
2b
2a
9ab
9ba
4
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
3
6
3
6
3
6
3
6
96
87
95
92
87
89
92
87
960
870
950
920
870
890
920
870
8b
8b
5
2b
2a
2b
2a
2b
2a
2b
9bb
9ca
6
8c
8c
7
9cb
9da
8
8d
8d
9
9 db
9ea
10
11
8e
8e
General procedure for the recy-
cling of nanosized MCM-41-Pd
The reaction was conducted by
using the procedure described pre-
viously under the reaction condi-
tions shown in Table 7. 50 mg of
catalyst was employed for all the
entries, with the exception of
Entry 3, which used 100 mg of NS-
MCM-41-Pd. After the reaction, the
9eb
9 fa
9ga
12
13
2a
2a
0.1
0.1
3
3
96
98
960
980
8 f
catalyst
was
collected
by
8g
centrifugation, washed alternately
with 3m HCl aqueous solution and
THF twice (10 mL for each wash),
and dried under vacuum over-
night. The recovered catalyst was
then reused in the same reaction
under identical conditions. The
[a] Reaction conditions: 8 (2.8 mmol), 2a (5.6 mmol), NS-MCM-41-Pd (20 mg), [PPh3]:[Pd]=2/1, THF, 508C.
[b] Isolated yields. [c] In the absence of PPh3. [d] 28 mmol of 8 and 56 mmol of 2 were used.
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Table 6. Nanosized MCM-41-Pd-catalyzed Negishi coupling of acyl chlorides with alkyl and alkynylzinc chloride.[a]
Entry
1
Acyl chloride
Organozinc chloride
t
[h]
Product
Yield
[%][b]
TON
850
n-C4H9ZnCl
3
3
85
75
48
50
60
47
4b
8a
8b
8c
8d
10ab
10bb
10cb
10 db
2
3
4
5
6
4b
4b
4b
4b
4b
750
480
500
600
470
6
3
3
8e
10eb
10 fb
12
8 f
8a
7
6
6
6
6
6
58
60
56
71
68
580
600
560
710
680
6a
6a
11aa
11 ba
11 ca
11 da
11 ea
8
8b
8c
8d
8e
9
6a
6a
6a
10
11
[a] Reaction conditions: 1 (2.8 mmol), 2a (5.6 mmol), NS-MCM-41-Pd (20 mg, 0.1 mol%), [PPh3]:[Pd]=2:1, THF, 508C. [b] Isolated yields.
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Entry Organo- Organozinc [Pd]
t
Yield [%][b] in each recycle
halide
chloride
[mol%] [h] 1st
2nd
3rd
4th
1[c]
2[c]
3[c,d]
4[e]
5[e]
6[e]
1a
1a
1a
8a
8a
8a
2a
4a
6c
2a
4b
6a
0.1
0.1
1
0.1
0.1
0.1
3
3
97
82
95
82
92
94
80
56
91
79
92
90
77
50
87
75
89
84
72
42
24 95
3
3
6
94
82
58
[a] Reaction conditions: 1 or 8 (7 mmol), 2, 4, or 6 (14 mmol), NS-MCM-
41-Pd (50 mg, 0.1 mol%), [PPh3]:[Pd]=2:1, THF. [b] Isolated yields.
[c] 708C. [d] 1a (1.4 mmol), 6c (2.8 mmol), NS-MCM-41-Pd (100 mg,
1 mol%), [PPh3]:[Pd]=2:1, THF. [e] At 508C.
product in each cycle was isolated from the collected solution by
the usual workup procedures.
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Acknowledgements
This research was financially supported by the National Science
Council of Taiwan (NSC95-2113M-027-001).
Keywords: halides · heterogeneous catalysis · mesoporous
materials · Negishi coupling · palladium
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Published online on October 10, 2012
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