Efficient Heterogeneous Gold(I)-Catalyzed Direct C(sp2)–C(sp) Bond Functionalization of Arylalkynes through a Nitrogenation Process to Amides

Article abstract of DOI:10.1002/adsc.201700783

The first heterogeneous gold(I)-catalyzed direct C(sp²)–C(sp) bond functionalization of arylalkynes through a nitrogenation process to amides has been achieved by using an ordered mesoporous silica (MCM-41)-immobilized phosphine gold(I) complex [MCM-41-PPh₃-AuCl] as catalyst and silver carbonate (Ag₂CO₃) as cocatalyst with trimethylsilyl azide (TMSN₃) as a nitrogen source, yielding a variety of amides in moderate to excellent yields under mild conditions. This heterogeneous phosphine gold(I) complex shows the same turnover numbers as the homogeneous chloro(triphenylphosphine)gold(I) (Ph₃PAuCl) and can easily be recovered by simple filtration of the reaction solution and recycled at least eight times without significant loss of activity, providing a novel, efficient, practical and economic method for the synthesis of amides from alkynes. (Figure presented.).

Full text of DOI:10.1002/adsc.201700783

Title: Efficient Heterogeneous Gold(I)-Catalyzed Direct Csp2–Csp
Bond Functionalization of Arylalkynes Through A Nitrogenation
Process to Amides
Authors: Quan Nie, Feiyan Yi, Bin Huang, and Mingzhong Cai
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700783
Link to VoR: http://dx.doi.org/10.1002/adsc.201700783

10.1002/adsc.201700783
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Efficient Heterogeneous Gold(I)-Catalyzed Direct Csp2–Csp
Bond Functionalization of Arylalkynes Through A Nitroge-
nation Process to Amides
Quan Nie, Feiyan Yi, Bin Huang and Mingzhong Cai*
Key Laboratory of Functional Small Organic Molecule, Ministry of Education and College of Chemistry & Chemical
Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China
e-mail: mzcai@jxnu.edu.cn
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: The first heterogeneous gold(I)-catalyzed direct the same turnover numbers as the homogeneous chloro(tri-
Csp2–Csp bond functionalization of arylalkynes through a phenylphosphine)gold(I) (Ph3PAuCl) and can easily be
nitrogenation process to amides has been achieved by using recovered by simple filtration of the reaction solution and
an ordered mesoporous silica (MCM-41)-immobilized phos- recycled at least eight times without significant loss of
phine gold(I) complex [MCM-41-PPh3-AuCl] as catalyst and activity, providing a novel, efficient, practical and economic
silver carbonate (Ag2CO3) as cocatalyst with trimethylsilyl method for the synthesis of amides from alkynes.
azide (TMSN3) as a nitrogen source, yielding a variety of
amides in moderate to excellent yields under mild condi-
tions. This heterogeneous phosphine gold(I) complex shows
Keywords: gold; arylalkyne; amide; ordered mesoporous
silica (MCM-41); heterogeneous catalysis
The C–C bond cleavage of unstrained molecules
usually requires special driving forces such as chela-
tion assistants to form stable intermediates.[11] Despite
some progress made in transition-metal-mediated
cleavage of Csp2–Csp bonds, the direct Csp2–Csp bond
functionalization are mostly limited to aromatic
nitrile compounds[12] and catalytic Csp2–Csp bond
cleavage of arylalkynes has rarely been reported.
Homogeneous Au(I) or Au(III) complexes have
increasingly found uses as mild Lewis acid catalysts
for organic transformations requiring the activation of
π bonds in the past two decades.[13] To date, the gold-
catalyzed construction of carbon-carbon[14] and
carbon-heteroatom[15] bonds has successfully been
applied in organic synthesis. In contrast, the gold-
catalyzed carbon-carbon bond cleavage reactions
have received less attention.[16] It is well known that
applications of homogeneous gold catalysts remain a
challenge in large-scale syntheses and industrial
processes because they are quite expensive, cannot be
recycled, and difficult to separate from the product
mixture. Recycling of homogeneous catalysts is a
task of great economic and environmental importance
in chemical and pharmaceutical industries, especially
when expensive or toxic heavy metal complexes are
employed.[17] Immobilized catalysts have attracted
more and more attention because of the advantages of
Introduction
Amide bond formation is one of the most often used
reactions in the synthesis of natural products, phar-
maceuticals, fine chemicals, and polymers since
amide group is a key motif in chemistry and
biology.[1] A straightforward synthetic strategy for
amide bond formation is the dehydration coupling of
a carboxylic acid with an amine in the presence of a
coupling reagent or the reaction of activated carbo-
xylic acid derivatives with an amine.[2] Many
alternative methods, such as Beckmann rearrange-
ment,[3] catalytic acylation of amines with carboxylic
acids,[4] aminocarbonylation of aryl halides,[5]
oxidation of terminal alkynes,[6] oxidative amidation
of aldehydes with amines,[7] and dehydrogenative
amidation of alcohols with amines[8] have also
emerged to improve the synthesis of amides.
However, there is still scope for the development of a
novel, alternative protocol for amide bond formation.
The discovery of new reactions through direct C–C
bond functionalization remains a challenge owing to
the inertness of C–C bonds and competing C–H
activation[9] and examples of C–C bond activation are
much less common except for strained C–C bonds.[10]
1
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10.1002/adsc.201700783
Advanced Synthesis & Catalysis
high catalytic efficiency and easy recycling, which
are important for expensive or toxic heavy metal
catalysts and flow chemistry processes.[18] Despite
significant advances made on organic transformations
catalyzed by gold nanoparticles supported on various
matrices,[19] the supported gold complexes-catalyzed
reactions have received less attention thus far.[20] Re-
cently, mesoporous MCM-41 materials have emerged
as smart and promising supports with great industrial
potential for immobilization due to their outstanding
advantages such as extremely high surface areas,
combined with large and defined pore sizes of
mesoporous materials, compared with other solid
supports.[21] During recent years, some functionalized
MCM-41-immobilized palladium,[22] rhodium,[23]
molybdenum,[24] gold,[20a,e] and copper[25] complexes
have been successfully utilized as potentially green
and sustainable catalysts in organic synthesis. As a
part of our continuing interest in the development of
efficient heterogeneous catalysts for organic synthesis,
MCM-41-PPh3-AuCl complex as a gray powder, the
gold content of the complex was found to be 0.38
mmol g-1 according to the ICP-AES measurements.
[22d-f,25]
Scheme 2. Preparation of the MCM-41-PPh3-AuCl com-
plex.
herein we wish to report the synthesis of an
MCM-41-immobilized phosphine gold(I) complex
[MCM-41-PPh3-AuCl] and its successful application
to the direct Csp2–Csp bond functionalization of aryl-
alkynes with TMSN3 as a nitrogen source through a
nitrogenation process to amides (Scheme 1). This
heterogeneous gold(I) complex exhibits the same
turnover numbers as the homogeneous Ph3PAuCl,
and can easily be recovered by simple filtration of the
reaction solution and recycled at least eight times
without significant loss of activity.
The small angle X-ray powder diffraction (XRD)
patterns of the parent MCM-41 and the MCM-41-
PPh3-AuCl complex are illustrated in Figure 1. Small
angle X-ray diffraction of the parent MCM-41 gave
three peaks corresponding to hexagonally ordered
mesoporous phases. For the MCM-41-PPh3-AuCl, the
(100) reflection of the parent MCM-41 with decr-
eased intensity was remained after functionalization,
while the (110) and (200) reflections became weak
and diffuse, which may be mainly due to contrast
matching between the silicate framework and organic
moieties which are located inside the channels of
MCM-41. These results indicate that the structure of
the mesoporous MCM-41 remains unchanged
through the grafting procedure and the formation of
the catalyst has taken place preferentially inside the
pore system of MCM-41. The energy dispersive X-
ray spectroscopy (EDS) shows the elements present
in the material. EDS analysis of fresh MCM-41-PPh3-
AuCl complex indicates the presence of Si, O, C, N,
P, Cl and Au elements (Figure 2).
Scheme 1. Heterogeneous gold(I)-catalyzed direct trans-
formation of arylalkynes to amides.
Results and Discussion
(100)
Preparation of MCM-41-PPh3-AuCl Complex and
Optimization of Reaction Conditions
The MCM-41-PPh3-AuCl complex was prepared by a
simple two-step procedure from readily available
reagents as shown in Scheme 2. First, 1-(4-(diphenyl-
phosphino)phenyl)-3-(3-(triethoxysilyl)propyl)urea[26]
was condensed with the mesoporous material MCM-
41 in toluene at reflux for 24 h, followed by the
silylation with Me3SiCl in toluene at room
temperature for 24 h to give triphenylphosphine-
functionalized MCM-41 (MCM-41-PPh3). Then the
latter reacted with Me2SAuCl in dichloromethane
(DCM) at room temperature for 8 h to afford the
1
(110)
2
(200)
2
3
4
5
6
7
2 (degrees)
Figure 1. XRD patterns of the parent MCM-41 (1) and
MCM-41-PPh3-AuCl (2).
2
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10.1002/adsc.201700783
Advanced Synthesis & Catalysis
which indicating that the turnover numbers of the
MCM-41-PPh3-AuCl are comparable to that of
homogeneous analogue Ph3PAuCl. Finally, we
screened the amount of the immobilized gold(I)
catalyst and were pleased to find that when MCM-41-
PPh3-AuCl (20 mol%)/Ag2CO3 (20 mol%) were used
as the catalysts, the yield of 2a could be improved to
88% (entry 18). However, further increasing the
amount of the catalyst did not enhance the yield
obviously (entry 19). Thus, the optimized reaction
conditions for this transformation are the MCM-41-
PPh3-AuCl (20 mol%)/Ag2CO3 (20 mol%) in DCE
with TFA as an acid additive at 60 ºC under Ar for 12
h (entry 18).
Figure 2. Energy dispersive spectra (EDS) of MCM-41-
PPh3-AuCl.
Table 1. Optimization of the reaction conditions[a]
The MCM-41-PPh3-AuCl was then used as catalyst
for the direct Csp2–Csp bond functionalization of
arylalkynes through a nitrogenation process to amides.
Initially, we investigated the transformation of 1,2-
diphenylethyne (1a) to N,2-diphenylacetamide (2a) in
the presence of TMSN3 as a nitrogen source to
optimize reaction conditions and the results are
summarized in Table 1. At first, the catalyst effect
was examined in DCE as solvent with TFA as an acid
additive (Table 1, entries 1-5). The MCM-41-PPh3-
AuCl complex afforded a low yield of 2a in the
absence of a silver salt as a co-catalyst (entry 1),
whilst use of Ag2CO3 alone as catalyst was ine-
ffective (entry 2). However, a combination of MCM-
41-PPh3-AuCl (10 mol%) and Ag2CO3 (10 mol%)
gave 2a in 73% yield (entry 3). The use of 10 mol%
of MCM-41-PPh3-AuCl/AgOAc as catalysts proved
to be also effective for this transformation and a
better yield was obtained with 10 mol% of MCM-41-
PPh3-AuCl/Ag(O2CCF3) as catalysts (entries 4 and 5),
indicating that the active gold catalytic species should
be MCM-41-PPh3-Au(O2CCF3). We also prepared
the MCM-41-PPh3-Au(O2CCF3) complex by reaction
of MCM-41-PPh3-AuCl with AgO2CCF3 in DCM at
room temperature for 1 h. When MCM-41-PPh3-
Au(O2CCF3) (10 mol%) alone was used as catalyst,
the reaction run in TFA/DCE medium afforded 2a in
74% yield, whilst the same reaction in DCE without
TFA gave a trace of 2a. These results showed that
TFA as an acid additive was necessary and the silver
salt did not affect the system. However, considering
the cost, we choose to use Ag2CO3 as co-catalyst.
Control experiments showed that MCM-41-PPh3-
AuCl complex is essential for this amide formation
reaction (entry 6). Our next studies focused on the
effect of acid additive on the model reaction and a
significant acid additive effect was observed. When
the reaction was carried out in the absence of TFA,
only a trace amount of 2a was detected (entry 7),
while other acid additives such as HOTf, HNTf2 and
HOAc were substantially less effective (entries 8-10).
The solvent effect was also examined (entries 11-15).
The use of TFA, HOAc, DCM and PhCl as the
solvent resulted in low yields and THF was
inefficient. When homogeneous Ph3PAuCl (10
mol%)/Ag2CO3 (10 mol%) were used as the catalysts,
the desired 2a was obtained in 72% yield (entry 16),
Yield
Entry
Silver salt (mol%) Acid
Solvent
[%][b]
19
1
–
TFA
TFA
TFA
TFA
TFA
TFA
–
HOTf DCE
HNTf2 DCE
HOAc DCE
TFA
TFA
TFA
TFA
TFA
TFA
TFA
TFA
TFA
DCE
DCE
DCE
DCE
DCE
DCE
DCE
2[c]
3
Ag2CO3 (10)
Ag2CO3 (10)
AgOAc (10)
Ag(O2CCF3) (10)
–
0
73
71
75
0
trace
19
14
trace
59
18
42
15
0
4
5
6[c]
7
8
9
10
11
12
13
14
15
16[d]
17[e]
18[f]
19[g]
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (10)
Ag2CO3 (5)
Ag2CO3 (20)
Ag2CO3 (30)
TFA
HOAc
PhCl
DCM
THF
DCE
DCE
DCE
DCE
72
45
88
89
[a] Reaction conditions: 1a (0.5 mmol), TMSN3 (1.0 mmol),
H2O (1.0 mmol), acid (200 μL) in solvent (2 mL), stirred at
60 ºC under Ar for 12 h. [b] Isolated yield. [c] Without MCM
[d]
[e]
-41-PPh3-AuCl.
Ph3PAuCl (10 mol%) was used.
5
mol% MCM-41-PPh3-AuCl was used. [f] 20 mol% MCM-
41-PPh3-AuCl was used. [g] 30 mol% MCM-41-PPh3-AuCl
was used.
Scope of the Reaction Catalyzed by MCM-41-
PPh3-AuCl Complex
With this promising result in hand, we started to
investigate the scope of heterogeneous gold(I)-
catalyzed direct Csp2–Csp bond functionalization of
arylalkynes under the optimized conditions and the
results are summarized in Table 2. As shown in Table
2, a range of symmetrical 1,2-diarylacetylenes 1b-1e
3
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10.1002/adsc.201700783
Advanced Synthesis & Catalysis
were found to be compatible with this protocol and
the reactions generated the corresponding substituted
N,2-diphenylacetamides 2b-2e in moderate to high
yields. Both electron-donating and electron-with-
drawing groups were tolerated well, but a strong
electron-donating group such as methoxy on the aryl
ring decreased the yield. When unsymmetrical 1,2-
diarylacetylenes bearing both electron-rich and
electron-deficient aromatic substituents were used as
the substrates, the azide anion preferred to add at the
electron-rich side of the diarylacetylenes, thus leading
to the formation of a complex mixture due to poor
regioselectivity. The reaction of the (cyclohex-1-en-
1-ylethynyl)benzene also resulted in the formation of
a complex mixture due to the presence of two
different Csp2–Csp bonds. Importantly, besides diaryl-
acetylenes, 1-alkyl-2-arylacetylenes 1f-1n proved to
be also suitable substrates and underwent highly
selective Csp2–Csp bond cleavage reaction effectively
to afford the desired amides 2f-2n in moderate to
good yields. Cycloalkyl groups and aryl groups
having different electronic natures could be tolerated.
Interestingly, sterically hindered 1-(3,3-dimethylbut-
1-ynyl)-4-methoxybenzene 1n could also give the
desired product 2n in moderate yield. It is noteworthy
that no amide products from Csp3–Csp bond cleavage
were detected in all these cases and aliphatic alkynes
were unreactive. Unfortunately, electron-deficient
internal alkynes such as ethyl 3-phenylpropiolate and
1,3-diphenylprop-2-yn-1-one did not work under
these conditions.
the method by varying internal alkynes to terminal
alkynes and the results are listed in Table 3. When the
reaction of phenylacetylene 3a was carried out at
60 °C in DCE in the presence of 10 mol% of MCM-
41-PPh3-AuCl/Ag2CO3 as catalysts, the desired amide
4a was obtained in only 45% yield. To our delight,
the yield of 4a was improved to 77% by replacing
DCE with TFA as solvent. Based on this result, TFA
was chosen as the solvent for the reaction of terminal
arylalkynes. As shown in Table 3, in the presence of
10 mol% of MCM-41-PPh3-AuCl/Ag2CO3, the reac-
tions of a variety of substituted phenylacetylenes 3b-
3t proceeded smoothly in TFA at 60 °C to give the
corresponding N-arylacetamides 4b-4t in good to
excellent yields. A wide range of substituents, inclu-
ding electron-donating groups, such as methyl (4b, 4o
and 4s), methoxy (4c), ethyl (4d), n-butyl (4e),
cyanomethyl (4f), and phenyl (4g), and electron-
withdrawing groups, such as fluoro (4h, 4p and 4t),
chloro (4i, 4q and 4s), bromo (4j), cyano (4k),
carboxy (4l), trifluoromethyl (4m), ester (4n), and
nitro (4r), were tolerated at the para, meta, and ortho
positions of the aromatic ring. It is noteworthy that
under the optimized conditions, halogens were
tolerated on the aromatic ring, and the obtained amide
products 4h-4j, 4p, 4q, 4s and 4t could be easily
transferred into their new derivatives by carbon–
halogen bond activation and its cross-coupling
reaction. In addition to terminal arylalkynes, a hetero-
arylacetylene 3-ethynylthiophene 3u was also
suitable substrate and gave the desired N-(thien-3-yl)-
acetamide 4u in moderate yield.
Table 2. Heterogeneous gold(I)-catalyzed direct transfor-
mation of arylalkynes 1 to amides 2.[a,b]
Table 3. Heterogeneous gold(I)-catalyzed direct transfor-
mation of terminal arylalkynes 3 to amides 4.[a,b]
[a] Reaction conditions: 1 (0.5 mmol), TMSN3 (1.0 mmol),
H2O(1.0 mmol), MCM-41-PPh3-AuCl(0.1 mmol), Ag2CO3
(0.1 mmol), TFA (200 μL) in DCE (2 mL), stirred at 60 ºC
under Ar for 12 h. [b] Isolated yield.
[a] Reaction conditions: 3 (0.5 mmol), TMSN3 (1.0 mmol),
H2O (1.0 mmol), MCM-41-PPh3-AuCl (0.05 mmol),
Encouraged by the above results obtained, we
further investigated the scope and the generality of
4
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10.1002/adsc.201700783
Advanced Synthesis & Catalysis
Ag2CO3 (0.05 mmol), in TFA (2 mL), stirred at 60 ºC
under Ar for 12 h. [b] Isolated yield.
For the practical application of a supported
precious metal catalyst system, it is important to
examine its ease of separation, good of recoverability
and reusability. The MCM-41-PPh3-AuCl can be
easily separated and recovered by a simple filtration
of the reaction solution. We next examined the
recycling of the catalyst by using the direct trans-
formation of 1,2-bis(4-methylphenyl)acetylene 1b to
amide 2b. After completion of the reaction, the
catalyst was recovered by simple filtration and
washed with NH3·H2O (2 × 5 mL), distilled water (2
× 5 mL), and ethanol (2 × 5 mL). After being air-
dried, it can be reused directly without further puri-
fication. The recovered gold catalyst was used in the
next run, and almost the same yield of 2b was
observed for eight consecutive cycles (Figure 3). It is
noteworthy that the reaction catalyzed by the
recovered catalyst didn’t need the addition of Ag2CO3
as a co-catalyst because the MCM-41-PPh3-AuCl had
been changed to the MCM-41-PPh3-Au(O2CCF3)
after the first cycle.
To ensure that the high activity of MCM-41-PPh3-
AuCl arises from the gold sites on the channel walls
and not from the leached gold species, the hetero-
geneity of MCM-41-PPh3-AuCl was first tested by
hot filtration.[27] For this, the reaction of diphenyl-
acetylene 1a was carried out until a conversion of
about 30%. Then the catalyst was separated from the
solution by filtration at 60 °C and the filtrate was
allowed to react further. We found that, after this hot
filtration, no significant increase in conversion was
observed, indicating that the leaching of gold from
the MCM-41 support is not a serious concern. It was
confirmed by ICP-AES analysis that no gold species
could be detected in the filtrate (below the detection
limit). These results rule out any contribution to the
observed activity from a homogeneous gold species
demonstrating that the observed catalysis was intrin-
sically heterogeneous.
100
80
60
40
20
0
A plausible mechanism for heterogeneous gold(I)-
catalyzed direct transformation of arylalkynes to
amides is illustrated in Scheme 3.[28] Initially,
arylalkyne is activated by the MCM-41-PPh3-
Au(O2CCF3) generated in situ from MCM-41-PPh3-
AuCl, Ag2CO3 and TFA to afford an MCM-41-
anchored phosphine-Au(I) alkyne complex (A). Then,
the nucleophilic attack by an azide anion on inter-
mediate (A) gives an MCM-41-anchored vinylgold
intermediate (B). The protonolysis of intermediate
(B) produces alkenyl azide intermediate (C) with
concurrent regeneration of the gold(I) catalyst.
Subsequent protonation of intermediate (C) forms
resonance azide cations (D1) and (D2), which could
undergo an acid-catalyzed rearrangement process to
afford the desired amide (E). It should be noted that
the electrophiles Au+ and H+ add preferentially at the
less substituted carbon atoms of the unsaturated C–C
triple and double bonds, respectively, (in interme-
diates A and C) in accordance with Markovnikov’s
rule.[29]
1
2
3
4
5
6
7
8
Recycling times
Figure 3. Recycle of the MCM-41-PPh3-AuCl catalyst.
Conclusions
In conclusion, we have developed a highly efficient
and recyclable MCM-41-immobilized phosphine
gold(I) catalyst for the direct Csp2–Csp bond functio-
nalization of arylalkynes through a nitrogenation
process to amides with TMSN3 as a nitrogen source.
The heterogeneous nitrogenation process of aryl-
alkynes generates a variety of amides in moderate to
excellent yields under mild conditions. This hetero-
geneous phosphine gold(I) catalyst exhibits the same
turnover numbers as the homogeneous Ph3PAuCl and
can easily be recovered by a simple filtration of the
reaction solution, and recycled at least eight times
without significant loss of activity. The use of MCM-
41-PPh3-AuCl complex as catalyst not only solves the
basic problems of catalyst separation and recovery,
but also avoids the addition of Ag2CO3 in recycling
process. This makes our protocol facile, economical,
and environmentally benign.
Scheme 3. Proposed catalytic cycle.
5
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10.1002/adsc.201700783
Advanced Synthesis & Catalysis
Experimental Section
added to the mixture. Then the catalyst was separated by
filtration of the reaction solution, washed with NH3·H2O (2
× 5 mL), distilled water (2 × 5 mL), and ethanol (2 × 5
mL), and reused in the next run. The organic layer of the
filtrate was washed with water (2 × 10 mL), dried over
anhydrous MgSO4 and concentrated under reduced
pressure. The residue was purified by chromatography on
silica gel (eluent: light petroleum ether/ethyl acetate) to
afford the amide product 2.
General Comments
All chemicals were reagent grade and used as purchased.
All solvents were dried and distilled before use. The
mesoporous MCM-41[21a] and 1-(4-(diphenylphosphino)-
phenyl)-3-(3-(triethoxysilyl)propyl)urea[26] were prepared
according to the literature methods. The products were
purified by flash chromatography on silica gel. Mixture of
EtOAc and light petroleum ether was generally used as
eluent. All products were characterized by comparison of
their spectra and physical data with authentic samples. IR
General Procedure for the Heterogeneous Gold(I)-
Catalyzed Transformation of Terminal Alkynes to
Amides.
1
spectra were recorded on an FT-IR spectrometer. H and
MCM-41-PPh3-AuCl (132 mg, 0.05 mmol), Ag2CO3 (0.05
mmol), H2O (1.0 mmol), TFA (2 mL), and terminal alkyne
3 (0.5 mmol) were added in turn to a oven-dried Schlenk
tube with a magnetic stir bar under Ar at 60 ºC. Then
TMSN3 (1.0 mmol) was added in two portions, once 0.5
mmol every 1 hour. The reaction mixture was stirred at 60
ºC over night. After being cooled to room temperature,
water (5 mL) and ethyl acetate (20 mL) were added to the
mixture. Then the catalyst was separated by filtration of
the reaction solution, washed with NH3·H2O (2 × 5 mL),
distilled water (2 × 5 mL), and ethanol (2 × 5 mL), and
reused in the next run. The organic layer of the filtrate was
washed with water (2 × 10 mL), dried over anhydrous
MgSO4 and concentrated under reduced pressure. The
residue was purified by chromatography on silica gel
(eluent: light petroleum ether/ethyl acetate) to afford the
amide product 4.
13C NMR spectra were recorded at 400 or 100 MHz with
CDCl3 or DMSO-d6 as the solvent and TMS as an internal
standard. Chemical shifts are reported in δ (ppm) relative
to TMS. HRMS spectra were recorded on a Q-Tof spectro-
meter with micromass MS software using electrospray
ionization (ESI). Melting points are uncorrected. Gold
content was determined with inductively coupled plasma
atom emission spectrometry (ICP-AES). X-ray diffraction
(XRD) measurements were carried out at room tempera-
ture using an X-ray powder diffractmeter. X-ray energy
dispersive spectroscopy (EDS) was performed using a
microscope.
Preparation of MCM-41-PPh3-AuCl Complex
1-(4-(Diphenylphosphino)phenyl)-3-(3-(triethoxysilyl)pro-
pyl)urea (0.788 g, 1.5 mmol) was added to a suspension of
2.2 g of the MCM-41 in 120 mL of dry toluene. The
mixture was then stirred at reflux for 24 h under an
atmosphere of argon. The solid material obtained was
filtered, washed with CHCl3 (2 × 20 mL), and dried in
vacuum at 140 °C for 3 h. The dried white solid was then
soaked in a solution of 3.0 g of Me3SiCl in 90 mL of dry
toluene at 25 °C under stirring for 24 h. The product was
filtered, washed with acetone (3 × 20 mL), and dried in
vacuum at 110 °C for 6 h to afford 2.715 g of hybrid
material MCM-41-PPh3. The phosphine content was found
to be 0.43 mmol g-1 by elemental analysis.
Acknowledgements
We thank the National Natural Science Foundation of China (No.
21462021), the Natural Science Foundation of Jiangxi Province
of China (No. 20161BAB203086) and Key Laboratory of
Functional Small Organic Molecule, Ministry of Education (No.
KLFS-KF-201409) for financial support.
In a small Schlenk tube, 1.1 g of the MCM-41-PPh3 was
mixed with Me2SAuCl (125 mg, 0.42 mmol) in 40 mL of
dry CH2Cl2. The mixture was stirred at room temperature
for 8 h under an atmosphere of argon. The solid product
was filtered, washed with CH2Cl2 (2 × 10 mL), and dried at
80 °C under vacuum for 5 h to afford 1.145 g of a gray
gold complex (MCM-41-PPh3-AuCl). The gold content
was found to be 0.38 mmol g-1 by ICP-AES.
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Advanced Synthesis & Catalysis
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