A heterogeneous gold(I)-catalyzed regioselective hydration of propargyl acetates toward α-acyloxy methyl ketones

Article abstract of DOI:10.1016/j.jorganchem.2020.121136

A heterogeneous gold(I)-catalyzed regioselective hydration of propargyl acetates has been developed that proceeds smoothly in 1,4-dioxane at room temperature in the presence of 1 mol% diphenylphosphine-modified MCM-41-anchored gold(I) complex [Ph₂P-MCM-41-AuSbF₆] as catalyst and provides an efficient and practical approach for the synthesis of a variety of α-acyloxy methyl ketones with high atom economy, good to excellent yield, and high functional group tolerance. This new immobilized gold(I) catalyst can readily be obtained by a simple preparative procedure from commercially available reagents, and recovered via a filtration process and reused at least seven times without apparent loss of activity.

Full text of DOI:10.1016/j.jorganchem.2020.121136

Journal Pre-proof
A heterogeneous gold(I)-catalyzed regioselective hydration of propargyl acetates
toward α-acyloxy methyl ketones
Yingying Du, Fang Yao, Rongli Zhang, Mingzhong Cai
PII:
S0022-328X(20)30037-1
DOI:
https://doi.org/10.1016/j.jorganchem.2020.121136
JOM 121136
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 14 September 2019
Revised Date: 15 January 2020
Accepted Date: 23 January 2020
Please cite this article as: Y. Du, F. Yao, R. Zhang, M. Cai, A heterogeneous gold(I)-catalyzed
regioselective hydration of propargyl acetates toward α-acyloxy methyl ketones, Journal of
Organometallic Chemistry (2020), doi: https://doi.org/10.1016/j.jorganchem.2020.121136.
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A heterogeneous gold(I)-catalyzed regioselective hydration
of propargyl acetates toward α-acyloxy methyl ketones
Yingying Du,a Fang Yao,b Rongli Zhang,a Mingzhong Caia*
a Key Laboratory of Functional Small Organic Molecule, Ministry of Education and
College of Chemistry & Chemical Engineering, Jiangxi Normal University, Nanchang
330022, P. R. China
b College of Chemical and Material Engineering, Quzhou University, Quzhou 324000,
P. R. China
ABSTRACT
A heterogeneous gold(I)-catalyzed regioselective hydration of propargyl acetates
has been developed that proceeds smoothly in 1,4-dioxane at room temperature in the
presence of 1 mol% diphenylphosphine-modified MCM-41-anchored gold(I) complex
[Ph2P-MCM-41-AuSbF6] as catalyst and provides an efficient and practical approach
for the synthesis of a variety of α-acyloxy methyl ketones with high atom economy,
good to excellent yield, and high functional group tolerance. This new immobilized
gold(I) catalyst can readily be obtained by a simple preparative procedure from com-
mercially available reagents, and recovered via a filtration process and reused at least
seven times without apparent loss of activity.
Keywords: Gold; Hydration; Propargyl acetate; Methyl ketone; Heterogeneous
catalysis
1. Introduction
The hydration of alkynes has provided a straightforward, atom-economical and
environmentally friendly method for the construction of diverse ketones and is
considered to be one of the most important C–O bond formation reactions in organic
*Corresponding author. Fax: +86 791 88120388.
1
E-mail address: mzcai@jxnu.edu.cn (M. Cai).

synthesis due to the wide availability of starting alkynes and the incorporation of
readily modifiable carbonyl functional moiety in the molecules [1-3]. Traditionally,
hydration of alkynes was conducted in the presence of highly toxic mercury salts or
more than stoichiometric amount of concentrated sulfuric acid [4-7]. Although some
Brønsted acids have also proven to exhibit catalytic activity for this transformation, in
most cases stoichiometric or excess amounts of acids were still required to achieve
high conversions [8-10]. To overcome the drawbacks of traditional alkyne hydration,
a variety of transition-metal complexes such as Fe [11], Co [12], Ag [13], Pt [14], Pd
[15], Ir [16], Ru [17], and Au [18-30] have been explored as catalysts for the reaction.
Among them, cationic gold catalysts display unique catalytic efficiency and have
attracted much attention because they exhibit strong affinity to activate the π bonds of
alkynes by nucleophilic attack. Recently, cationic gold(I) complexes have proven to
be one of the most promising catalysts for the regioselctive hydration of terminal
alkynes owing to their high activity and regioselectivity [21-29]. Cationic gold(I)
catalysts are usually prepared in situ by the reaction of neutral gold(I) complexes
[LAuCl, L = phosphine or N-heterocyclic carbene] with various silver salts [AgOTf,
AgNTf2, AgBF4, AgSbF6, etc], which suffers from some drawbacks such as high cost
and the light sensitivity of silver salts. In contrast, silver salt-free heterogeneous gold
catalysts for the hydration of alkynes have received less attention [31-33].
It was reported that the existence of a neighboring ester group in alkynes, e.g.,
propargyl carboxylates, would result in regioselective incorporation of the carbonyl
functional moiety in the product molecules through gold-catalyzed hydration [34,35].
2

Recently, Sahoo and coworkers reported gold(I)-catalyzed regioselective hydration of
propargyl acetates by using Ph3PAuCl and AgSbF6 as catalysts, providing α-acyloxy
methyl ketones in good to excellent yields under mild conditions [36]. The hydration
products could be converted into α-hydroxy methyl ketones in a straightforward
manner, and the latter are important synthetic intermediates for various bioactive
compounds and are found in many natural products of pharmacological importance
[37-39]. Besides, the Ph3PAuCl/AgSbF6 system has also been applied to regioselective
hydration of terminal halo-substituted propargyl carboxylates leading to α-acyloxy
α'-halo ketones [40]. Although this homogeneous gold(I) catalytic system is highly
efficient for the regioselective hydration of propargyl carboxylates towards various
valuable functionalized methyl ketones, the non-recyclability of expensive homo-
geneous Ph3PAuCl and the decay of cationic gold as well as the light sensitivity of
AgSbF6 make this method of limited synthetic utility. Thus, development of a
recyclable heterogeneous gold(I) catalyst having a high catalytic efficiency for the
regioselective hydration of propargyl carboxylates is highly desirable from both
economical and environmental points of view.
The hexagonally-ordered mesoporous silica MCM-41 has been widely employed as
an ideal solid support for anchoring various homogeneous metal catalysts because it
possesses ultrahigh surface area, large and uniform pore size, big pore volume and
excellent thermal stability [41-43]. To date, some functionalized MCM-41-anchored
gold(I) and gold(III) complexes have been successfully utilized in many organic
reactions as green and sustainable gold catalysts [44-50]. Recently, we have reported
3

the preparation of a diphenylphosphine-modified MCM-41-anchored gold(I) complex
[Ph2P-MCM-41-AuCl] and its successful application to regiospecific hydroamina-
tion of ynamides and propiolic acid derivatives with anilines [51]. Considering our
continued interest in the development of efficient and recyclable gold catalysts for
organic transformations [49-51], herein we report a highly efficient, heterogeneous
gold(I)-catalyzed regioselective hydration of propargyl acetates towards α-acyloxy
methyl ketones by using the diphenylphosphine-modified MCM-41-anchored gold(I)
complex [Ph2P-MCM-41-AuSbF6] as the catalyst, which could be facilely prepared
by treating Ph2P-MCM-41-AuCl with AgSbF6 in dichloromethane (DCM) at room
temperature for 0.5 h (Scheme 1). This supported gold(I) catalyst displays high
catalytic efficiency in this transformation and can be readily separated and recovered
from the reaction mixture via a simple filtration process, and its catalytic activity
remains almost unaltered even after being recycled for 8 times.
2. Results and discussion
2.1. Heterogeneous gold(I)-catalyzed regioselective hydration of propargyl acetates.
Four diphenylphosphine-modified MCM-41-anchored gold(I) complexes [Ph2P-
MCM-41-AuX, X = OTf, NTf2, SbF6, and BF4] were facilely prepared by the reaction
of the known Ph2P-MCM-41-AuCl complex [51] with various silver salts (AgX =
AgOTf, AgNTf2, AgSbF6, and AgBF4) in DCM at room temperature for 0.5 h, as
shown in Scheme 2. Their characterization data were given in the Supporting
Information. They were then used as the catalysts for regioselective hydration of
4

propargyl acetates. In our initial screening experiments, 1-phenylprop-2-ynyl acetate
1a was chosen as the model substrate to optimize reaction conditions, and the results
are summarized in Table 1. At first, the effect of various heterogeneous gold catalysts
on the model reaction was examined in dioxane at room temperature (entries 1-5).
Ph2P-MCM-41-AuSbF6 was found to be the most effective for this reaction and the
use of 2 mol% Ph2P-MCM-41-AuSbF6 as catalyst afforded the desired product 2a in
97% isolated yield within 5 h (entry 3), while other heterogeneous gold complexes
such as Ph2P-MCM-41-AuOTf, Ph2P-MCM-41-AuNTf2, and Ph2P-MCM-41-AuBF4
provided relatively lower yields on longer reaction times (entries 1, 2 and 4) and
Ph2P-MCM-41-AuCl was ineffective (entry 5). Replacement of dioxane with CH2Cl2
or MeOH resulted in a decreased yield of 2a (entries 6 and 7), whilst the use of DMF
or DMSO as solvents did not produce 2a (entries 8 and 9). Finally, the amount of
Ph2P-MCM-41-AuSbF6 was also screened (entries 10 and 11). To our delight,
reducing the catalyst loading from 2 to 1 mol% did not affect the reaction efficiency
significantly and led to the hydration product 2a in 96% isolated yield (entry 10). But,
further reducing the amount of the gold catalyst to 0.5 mol% resulted in a slightly
decreased yield and a longer reaction time was required (entry 11). When a
homogenous Ph3PAuCl (1 mol%)/AgSbF6 (1 mol%) catalytic system was used in the
reaction, the desired 2a was also isolated in 97% yield, which indicating that the
catalytic efficiency of Ph2P-MCM-41-AuSbF6 was comparable to that of homogenous
Ph3PAuCl/AgSbF6 system (entry 12). Therefore, the optimum conditions for this
hydration reaction were the use of Ph2P-MCM-41-AuSbF6 (1 mol%) in dioxane as
5

solvent at room temperature under Ar for 12 h (Table 1, entry 10).
Having established the optimized reaction conditions, we started to investigate the
generality of this heterogeneous gold(I)-catalyzed hydration of the terminal alkynes of
propargyl acetates, and the results are summarized in Table 2. At first, the effect of the
electronic nature of substituents on the aryl moiety of 1-arylprop-2-ynyl acetates (1b-l)
on the hydration reaction was examined. 1-Arylprop-2-ynyl acetates (1b-e) bearing
various electron-donating groups, such as methyl, t-butyl, benzyloxy, and methoxy at
the 4- or 3-positions on the benzene ring, showed a similar reactivity with the electro-
nically neutral 1-phenylprop-2-ynyl acetate (1a) and underwent hydration smoothly to
give the corresponding hydrated products 2b-e in 89-94% yields. Besides, more
electron-rich substrate 1f provided the target product 2f in 90% yield. Furthermore,
electron-neutral substrate 1g having a rigid biphenyl group also reacted well to afford
2g in 90% yield. Electron-withdrawing substituents such as halo and trifluoromethyl
groups on the benzene ring did not affect the hydration reaction, and halo groups are
inert to the optimized conditions. The hydration reactions of electron-deficient
substrates 1h-l proceeded effectively to afford the desired products 2h-l in excellent
yields. These halo groups in products 2h-k are expected to be converted into other
useful functional groups through the cross-coupling reactions catalyzed by transition
metals. It is well known that protecting groups of the hydroxyl moiety are sensitive to
the mild acidic and basic conditions. To examine the relative stability of the protecting
groups under the optimized conditions, the hydration reaction of the substrate 1m
with a silyl ether unit was performed. To our delight, t-butyldimethylsilyl (TBS) as the
6

bulkier silyl protecting group was tolerated well in the reaction and the expected
product 2m was obtained in 81% yield.
We next examined the effect of ortho-substitution on the aryl moiety to hydration
reaction, and the results are also shown in Table 2. The ortho-allyloxy group did not
partake in the hydration reaction and the expected product 2n was produced in 95%
yield; the allyl functionality could undergo further organic transformations. Electron-
donating methoxy or acetyloxy groups at the 2-position did not inhibit the hydration
and provided the desired products 2o-q in excellent yields. The hydration of propargyl
acetates 1r-u bearing various electron-withdrawing ortho substituents, such as chloro,
bromo, and nitro groups, proceeded smoothly under the standard conditions to afford
the corresponding ketones 2r-u in 88-94% yields. Gratifyingly, bulky 1-(naphthalene-
1-yl)prop-2-ynyl acetate 1v also reacted quite well, furnishing the target product 2v in
93% yield. The above results indicated that electronic and steric effects of substituents
on the aromatic ring did not impart the significant effect to hydration of terminal triple
bond of propargyl acetates. Notably, thienyl-2-substituted propargyl acetate 1w could
undergo hydration effectively, affording 76% yield of 2w, but furyl-2-substituted
propargyl acetate did not deliver the desired methyl ketone. In addition to aryl- and
heteroaryl-substituted propargyl acetates, the hydration of alkyl-, vinyl-, dialkyl-, and
aryl/alkyl-substituted propargyl acetates was also investigated. As shown in Table 2,
alkyl-, benzyl- and cycloalkyl-substituted propargyl acetates 1x-b' underwent the
regioselective hydration reaction smoothly to give the corresponding methyl ketones
2x-b' in 84-93% yields. Interestingly, vinyl-substituted propargyl acetates 1c' and 1d'
7

were compatible with the standard conditions and afforded the desired α-acetyloxy-
β,γ-unsaturated methyl ketones 2c' and 2d', respectively in high yields. Besides,
sterically hindered substrate 1e' having a quaternary α-carbon center with two alkyl
groups also reacted well, thus furnishing the expected ketone 2e' in 93% yield.
Similarly, both aryl- and methyl-substituted propargyl acetates 1f' and 1g' did not
influence the reaction efficiency and gave the desired products 2f' and 2g' in 90-92%
yields. Notably, sterically hindered 1-ethynylcyclohexyl acetate 1h' also underwent
the hydration effectively to produce the target product 2h' in 86% yield.
2.2. Leaching test for Ph2P-MCM-41-AuSbF6
To confirm that the observed hydration reaction was due to the Ph2P-MCM-41-
AuSbF6 catalyst and not to a soluble gold species leached from this heterogeneous
catalyst, we focused on the hydration of 1-phenylprop-2-ynyl acetate 1a. After the
reaction was carried out for 4 h, the catalyst was removed from the reaction mixture
by filtration and the catalyst-free filtrate was stirred at room temperature under Ar for
another 10 h. It was found that no increase in conversion of 1-phenylprop-2-ynyl
acetate 1a was observed in the filtrate, indicating that the soluble gold species leached
from the catalyst (if any) are not related to the observed reaction. In addition, no gold
species could be detected in the filtrate based on ICP-AES analysis. The above results
indicated that the Ph2P-MCM-41-AuSbF6 complex was stable during the hydration
and is actually functioning in a heterogeneous manner.
2.3. Possible mechanism for the heterogeneous gold(I)-catalyzed regioselective
8

hydration reaction.
A possible mechanism for the heterogeneous gold(I)-catalyzed regioselective
hydration of propargyl acetates to α-acyloxy methyl ketones is illustrated in Scheme 3
[36]. Firstly, coordination of the Ph2P-MCM-41-AuSbF6 complex to alkyne moiety in
propargyl acetate 1 produces an MCM-41-bound gold(I)–alkyne–π complex
intermediate A. Then reactive intermediate A undergoes an intramolecular 5-exo-dig
attack of carbonyl oxygen on the acetylenic carbon to generate an MCM-41-bound
5-membered vinylgold cation intermediate B. Subsequent nucleophilic addition of
H2O to intermediate B forms another MCM-41-bound vinylgold cation intermediate
C. The latter undergoes the protodeauration to provide intermediate D and regenerate
the gold(I) catalyst. Finally, the isomerization of intermediate D occurs to furnish
α-acyloxy methyl ketone 2.
2.4. Recycling of the gold(I) catalyst
For practical application of a supported precious metal catalyst, its ease of separa-
tion, stability and reusability are important factors to be examined. Ph2P-MCM-41-
AuSbF6 can be readily separated and recovered from the reaction product via a simple
filtration process. We next examined the recyclability of the Ph2P-MCM-41-AuSbF6
catalyst in the hydration reaction of 1-phenylprop-2-ynyl acetate 1a. Upon completion
of the first reaction cycle, the Au(I) catalyst was recovered by filtration of the reaction
solution and washed with dioxane and acetone. After being air-dried, the recovered
gold(I) catalyst was employed in the next cycle using the same substrate under the
9

identical conditions, and the results are listed in Table 3. As shown in Table 3, the
target product 2a was produced in almost consistent yield for eight consecutive cycles,
which indicating that this heterogeneous gold(I) catalyst can be recycled at least eight
times without any significant decrease in catalytic efficiency. In order to determine if
the supported phosphine ligand was oxidized to the phosphine oxide during the
hydration reaction, both the recovered catalyst after eight consecutive cycles and the
fresh catalyst were subjected to hydrolysis under basic conditions and the silyl
31
31
attachments obtained were subjected to P NMR determination. P NMR spectrum
of the fresh catalyst (Fig. 1a) showed a strong signal at δ 33.2 ppm, which corres-
31
ponding to the phosphine in the diphenylphosphine gold(I) complex [52], whilst P
NMR spectrum of the recovered catalyst (Fig. 1b) also displayed only one signal at δ
32.5 ppm, which indicating that the oxidation of the phosphine ligand to the
phosphine oxide did not occur under the optimized reaction conditions. In addition,
the Au content of the recovered gold(I) catalyst after eight consecutive runs was
measured to be 0.36 mmol/g by ICP-AES analysis, which revealing negligible gold
leaching.
3. Conclusions
In summary, heterogenized homogeneous gold(I) catalyst [Ph2P-MCM-41-AuSbF6]
has been successfully developed for the regioselective hydration reaction of propargyl
acetates. It is demonstrated that such a heterogenized diphenylphosphine-gold(I)
complex is a highly efficient and recyclable heterogeneous catalyst for the synthesis
10

of a variety of α-acyloxy methyl ketones. The reaction was applicable to a wide range
of propargyl acetates with broad functional group compatibility and tolerance to
acid-labile protecting groups. This heterogeneous gold(I)-catalyzed hydration reaction
has some attractive features such as readily available starting materials, mild reaction
conditions, the absence of acidic promoter, good to excellent yields, and excellent
recyclability of the gold(I) catalyst, offering a simple, highly efficient, economic and
practical route to α-acyloxy methyl ketones, which would transform to synthetically
versatile α-hydroxy methyl ketones in a straightforward manner.
4. Experimental
4.1. General remarks
All starting chemicals were purchased from different commercial sources and
utilized as received without further purification. All solvents were purified by drying
and distillation before use. The products were isolated by using column chromato-
graphy on 230-400 mesh silica gel. A mixture of hexane and EtOAc was generally
used as eluent. 1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were recorded
31
on a Bruker Avance 400 NMR spectrometer in CDCl3 as solvent. P NMR spectra
(121 MHz) were recorded on a Bruker Avance 400 MHz spectrometer in CDCl3 as
solvent. Melting points are uncorrected. The content of gold was determined with a
Jarrell-Ash 1100 ICP. HRMS spectra were recorded on an AGILENT 6520 Accurate-
Mass QTOF LC/MS spectrometer using the electrospray mode (ES). Mesoporous
MCM-41 material [41] and propargyl acetates 1 [36] were prepared according to
11

literature methods.
4.2. Preparation of Ph2P-MCM-41-AuSbF6 complex [51].
A mixture of 2-(diphenylphosphino)ethyltriethoxysilane (0.566 g, 1.5 mmol) and
the MCM-41 (2.0 g) in dry toluene (130 mL) was stirred at 100 °C for 24 h under an
argon atmosphere. The product was collected by filtration, washed with chloroform
(25 mL), and dried in vacuo at 130 °C for 6 h. The resulting white powders were then
added to a solution of Me3SiCl (3.0 g) in dry toluene (110 mL) and the mixture was
stirred at room temperature under argon for 24 h. The solid product was isolated by
filtration, followed by washing with acetone (2 × 25 mL), and drying in vacuo at
110 °C for 5 h to provide 2.412 g of modified material Ph2P-MCM-41. The content of
phosphorus was determined to be 0.42 mmol g-1 by elemental analysis.
A mixture of Ph2P-MCM-41 (1.00 g) and Me2SAuCl (115 mg, 0.39 mmol) in dry
CH2Cl2 (30 mL) was stirred at room temperature for 8 h under an argon atmosphere.
The product was filtered off, washed with CH2Cl2 and then treated with AgSbF6 (134
mg, 0.39 mmol) in CH2Cl2 (30 mL) at room temperature for 0.5 h. The resulting
product was collected by filtration, washed with 25 wt% of NH3·H2O (2 × 20 mL),
distilled water (2 × 20 mL) and EtOH (2 × 20 mL), and dried in vacuo to afford 1.053
g of a gray gold complex (Ph2P-MCM-41-AuSbF6). The content of gold was found to
be 0.37 mmol g-1 based on ICP-AES.
The Ph2P-MCM-41-AuOTf, Ph2P-MCM-41-AuNTf2, and Ph2P-MCM-41-AuBF4
were also prepared by using Ph2P-MCM-41 (1.00 g), Me2SAuCl (115 mg, 0.39 mmol),
12

and AgX (X = OTf, SbNTf2 and BF4, 0.39 mmol) as the starting materials in the same
manner, the contents of gold were determined to be 0.38 mmol g-1, 0.35 mmol g-1 and
0.36 mmol g-1, respectively based on ICP-AES analysis.
4.3. General procedure for the heterogeneous gold(I)-catalyzed regioselective
hydration of propargyl acetates.
A Schlenk tube was charged with Ph2P-MCM-41-AuSbF6 (28 mg, 0.01 mmol),
propargyl acetate (1.0 mmol), deionized water (3.0 mmol) and 1,4-dioxane (1.5 mL)
under an argon atmosphere. The reaction mixture was stirred at room temperature for
12 h. Upon completion of the reaction, the mixture was diluted with EtOAc (10 mL)
and filtered. The gold(I) catalyst was washed with dioxane (2 × 3 mL) and acetone (2
× 3 mL), and reused in the next run. The filtrate was concentrated under reduced
pressure and the residue was purified by using column chromatography on silica gel
(eluent: hexane/ethyl acetate) to afford the desired product 2.
1
4.3.1. 2-Oxo-1-phenylpropyl acetate (2a) [36]. Colorless oil. H NMR (400 MHz,
13
CDCl3): δ 7.43-7.39 (m, 5H), 5.98 (s, 1H), 2.18 (s, 3H), 2.11 (s, 3H). C NMR (100
MHz, CDCl3): δ 201.7, 170.2, 133.2, 129.4, 129.1, 128.1, 80.9, 26.1, 20.7.
1
4.3.2. 2-Oxo-1-(p-tolyl)propyl acetate (2b) [36]. Colorless oil. H NMR (400 MHz,
CDCl3): δ 7.21 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 5.86 (s, 1H), 2.28 (s, 3H),
2.09 (s, 3H), 2.01 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.8, 170.3, 139.4, 130.2,
129.8, 128.1, 80.8, 26.1, 21.2, 20.7.
1
4.3.3. 1-(4-(tert-Butyl)phenyl)-2-oxopropyl acetate (2c). Colorless oil. H NMR (400
MHz, CDCl3): δ 7.42 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.4 Hz, 2H), 5.96 (s, 1H), 2.17
13

(s, 3H), 2.11 (s, 3H), 1.32 (s, 9H). 13C NMR (100 MHz, CDCl3): δ 201.8, 170.3, 152.6,
+
130.1, 127.9, 126.1, 80.8, 34.7, 31.2, 26.2, 20.7. HRMS calcd for C15H20O3 [M+]:
248.1412, found 248.1419.
4.3.4. 1-(4-(Benzyloxy)phenyl)-2-oxopropyl acetate (2d). Pale yellow solid. Mp
1
84.2-84.5 ºC. H NMR (400 MHz, CDCl3): δ 7.34-7.27 (m, 4H), 7.26-7.20 (m, 3H),
6.91 (d, J = 8.8 Hz, 2H), 5.84 (s, 1H), 4.97 (s, 2H), 2.07 (s, 3H), 2.00 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ 201.9, 170.4, 159.7, 136.6, 129.7, 128.7, 128.1, 127.5,
+
125.4, 115.5, 80.5, 70.1, 26.2, 20.7. HRMS calcd for C18H18O4 [M+]: 298.1205,
found 298.1203.
1
4.3.5. 1-(3-Methoxyphenyl)-2-oxopropyl acetate (2e) [36]. Pale yellow oil. H NMR
(400 MHz, CDCl3): δ 7.31 (t, J = 7.8 Hz, 1H), 7.00 (d, J = 7.6 Hz, 1H), 6.96-6.90 (m,
2H), 5.95 (s, 1H), 3.80 (s, 3H), 2.18 (s, 3H), 2.11 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 201.5, 170.1, 160.0, 134.6, 130.1, 120.3, 114.9, 113.4, 80.8, 55.3, 26.0,
20.6.
1
4.3.6. 1-(3,5-Dimethoxyphenyl)-2-oxopropyl acetate (2f). Pale yellow oil. H NMR
(400 MHz, CDCl3): δ 6.55 (d, J = 2.0 Hz, 2H), 6.47 (t, J = 2.2 Hz, 1H), 5.89 (s, 1H),
3.79 (s, 6H), 2.19 (s, 3H), 2.12 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.5, 170.1,
+
161.2, 135.2, 106.0, 101.2, 80.9, 55.4, 26.0, 20.7. HRMS calcd for C13H16O5 [M+]:
252.0998, found 252.0995.
4.3.7. 1-([1,1'-Biphenyl]-4-yl)-2-oxopropyl acetate (2g). Pale yellow solid. Mp
94.8-95.2 ºC. 1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 7.2
Hz, 2H), 7.40-7.32 (m, 4H), 7.28-7.25 (m, 1H), 5.93 (s, 1H), 2.10 (s, 3H), 2.05 (s, 3H).
14

13C NMR (100 MHz, CDCl3): δ 201.7, 170.3, 142.4, 140.2, 132.1, 128.9, 128.6, 127.8,
+
127.7, 127.2, 80.7, 26.2, 20.7. HRMS calcd for C17H16O3 [M+]: 268.1099, found
268.1091.
4.3.8. 1-(4-Fluorophenyl)-2-oxopropyl acetate (2h) [36]. Colorless oil. 1H NMR (400
MHz, CDCl3): δ 7.40 (dd, J = 8.8, 5.2 Hz, 2H), 7.10 (t, J = 8.6 Hz, 2H), 5.96 (s, 1H),
2.19 (s, 3H), 2.12 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.6, 170.1, 163.3 (d, J =
247.4 Hz), 129.9 (d, J = 8.4 Hz), 129.2 (d, J = 3.1 Hz), 116.1 (d, J = 21.6 Hz), 80.1,
26.1, 20.6.
4.3.9. 1-(4-Chlorophenyl)-2-oxopropyl acetate (2i) [36]. Colorless oil. 1H NMR (400
MHz, CDCl3): δ 7.54 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.8 Hz, 2H), 5.93 (s, 1H), 2.19
(s, 3H), 2.12 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.3, 170.1, 132.3, 129.6,
123.6, 80.2, 26.1, 20.7.
1
4.3.10. 1-(4-Bromophenyl)-2-oxopropyl acetate (2j) [36]. Pale yellow oil. H NMR
(400 MHz, CDCl3): δ 7.54 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.8 Hz, 2H), 5.93 (s, 1H),
2.19 (s, 3H), 2.12 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.4, 170.0, 135.4, 131.8,
129.3, 129.2, 80.1, 26.0, 20.6.
1
4.3.11. 1-(3,4-Dichlorophenyl)-2-oxopropyl acetate (2k) [36]. Pale yellow oil. H
NMR (400 MHz, CDCl3): δ 7.53 (d, J = 2.0 Hz, 1H), 7.49 (d, J = 8.4 Hz, 1H), 7.27
(dd, J = 8.2, 1.8 Hz, 1H), 5.92 (s, 1H), 2.21 (s, 3H), 2.15 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 201.1, 169.9, 133.7, 133.4, 133.3, 131.0, 129.7, 127.1, 79.4, 26.1, 20.6.
1
4.3.12. 2-Oxo-1-(3-(trifluoromethyl)phenyl)propyl acetate (2l). Colorless oil. H
NMR (400 MHz, CDCl3): δ 7.61 (s, 1H), 7.58-7.53 (m, 2H), 7.46 (t, J = 7.8 Hz, 1H),
15

5.94 (s, 1H), 2.13 (s, 3H), 2.06 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.3, 170.0,
134.4, 131.5 (q, J = 32.5 Hz), 131.2, 129.6, 126.1 (q, J = 3.6 Hz), 124.6 (q, J = 3.8
+
Hz), 123.7 (q, J = 270.8 Hz), 80.1, 26.0, 20.5. HRMS calcd for C12H11F3O3 [M+]:
260.0660, found 260.0665.
4.3.13. 1-(3-(tert-Butyldimethylsilyloxy)phenyl)-2-oxopropyl acetate (2m) [36]. Pale
brown oil. 1H NMR (400 MHz, CDCl3): δ 7.28-7.23 (m, 1H), 7.00 (d, J = 7.6 Hz, 1H),
6.89-6.84 (m, 2H), 5.91 (s, 1H), 2.19 (s, 3H), 2.10 (s, 3H), 0.99 (s, 9H), 0.20 (s, 6H).
13C NMR (100 MHz, CDCl3): δ 201.4, 170.2, 156.2, 134.5, 130.1, 121.0, 120.9, 119.7,
80.7, 26.0, 25.6, 20.7, 18.2, -4.4.
1
4.3.14. 1-(2-(Allyloxy)phenyl)-2-oxopropyl acetate (2n) [36]. Colorless oil. H NMR
(400 MHz, CDCl3): δ 7.35-7.31 (m, 2H), 6.99 (d, J = 7.6 Hz, 1H), 6.95 (dd, J = 8.6,
4.6 Hz, 1H), 6.51 (s, 1H), 6.09-6.00 (m, 1H), 5.43 (dd, J = 17.4, 1.2 Hz, 1H), 5.31 (dd,
J = 10.6, 1.0 Hz, 1H), 4.67-4.56 (m, 2H), 2.16 (s, 3H), 2.12 (s, 3H). 13C NMR (100
MHz, CDCl3): δ 201.9, 170.3, 155.9, 132.7, 130.6, 129.5, 122.3, 121.3, 117.8, 112.4,
75.0, 69.2, 26.3, 20.7.
4.3.15. 1-(2-Methoxyphenyl)-2-oxopropyl acetate (2o). Pale yellow oil. 1H NMR (400
MHz, CDCl3): δ 7.28-7.18 (m, 2H), 6.91-6.83 (m, 2H), 6.37 (s, 1H), 3.77 (s, 3H), 2.04
(s, 3H), 1.99 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.8, 170.2, 156.9, 130.7,
+
129.4, 122.0, 121.0, 111.2, 74.9, 55.6, 26.1, 20.7. HRMS calcd for C12H14O4 [M+]:
222.0892, found 222.0883.
1
4.3.16. 1-(2,5-Dimethoxyphenyl)-2-oxopropyl acetate (2p). Pale yellow oil. H NMR
(400 MHz, CDCl3): δ 6.81-6.77 (m, 3H), 6.36 (s, 1H), 3.75 (s, 3H), 3.66 (s, 3H), 2.08
16

(s, 3H), 2.02 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.7, 170.2, 153.8, 151.0,
+
122.7, 115.6, 114.6, 112.4, 74.7, 56.2, 55.7, 26.1, 20.7. HRMS calcd for C13H16O5
[M+]: 252.0998, found 252.0992.
1
4.3.17. 2-(1-Acetoxy-2-oxopropyl)phenyl acetate (2q). Pale yellow oil. H NMR (400
MHz, CDCl3): δ 7.39-7.35 (m, 2H), 7.25-7.19 (m, 1H), 7.09 (d, J = 8.0 Hz, 1H), 6.09
(s, 1H), 2.26 (s, 3H), 2.07 (s, 3H), 2.01 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 200.6,
170.0, 169.2, 149.0, 130.7, 130.4, 126.7, 126.1, 123.7, 76.1, 26.2, 20.8, 20.6. HRMS
+
calcd for C13H14O5 [M+]: 250.0841, found 250.0844.
1
4.3.18. 1-(2-Chlorophenyl)-2-oxopropyl acetate (2r) [36]. Pale yellow oil. H NMR
(400 MHz, CDCl3): δ 7.46 (dd, J = 7.6, 1.6 Hz, 1H), 7.40 (dd, J = 7.2, 2.4 Hz, 1H),
7.37-7.29 (m, 2H), 6.52 (s, 1H), 2.19 (s, 3H), 2.17 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 200.8, 170.0, 134.0, 131.5, 130.6, 130.1, 129.8, 127.5, 76.9, 26.7, 20.6.
4.3.19. 1-(2-Bromophenyl)-2-oxopropyl acetate (2s) [36]. Colorless oil. 1H NMR (400
MHz, CDCl3): δ 7.65 (d, J = 8.0 Hz, 1H), 7.40-7.33 (m, 2H), 7.28-7.23 (m, 1H), 6.51
(s, 1H), 2.19 (s, 3H), 2.18 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 200.9, 170.0, 133.4,
133.2, 130.9, 129.9, 128.1, 124.4, 79.2, 26.9, 20.6.
1
4.3.20. 1-(2,4-Dichlorophenyl)-2-oxopropyl acetate (2t) [36]. Pale yellow oil. H
NMR (400 MHz, CDCl3): δ 7.48 (d, J = 2.0 Hz, 1H), 7.35 (d, J = 8.4 Hz, 1H), 7.30
(dd, J = 8.4, 2.0 Hz, 1H), 6.45 (s, 1H), 2.19 (s, 3H), 2.18 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 200.5, 169.8, 136.0, 134.6, 130.6, 130.2, 129.9, 127.9, 76.3, 26.7, 20.5.
1
4.3.21. 1-(2-Nitrophenyl)-2-oxopropyl acetate (2u). Pale yellow oil. H NMR (400
MHz, CDCl3): δ 8.07 (d, J = 8.0 Hz, 1H), 7.67 (t, J = 7.6 Hz, 1H), 7.58-7.52 (m, 2H),
17

6.74 (s, 1H), 2.32 (s, 3H), 2.20 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 200.7, 169.5,
148.1, 133.8, 130.1, 129.9, 129.7, 125.2, 75.7, 27.1, 20.6. HRMS calcd for
+
C11H11NO5 [M+]: 237.0637, found 237.0632.
1
4.3.22. 1-(Naphthalen-1-yl)-2-oxopropyl acetate (2v) [36]. Pale yellow oil. H NMR
(400 MHz, CDCl3): δ 8.02 (d, J = 8.4 Hz, 1H), 7.77-7.73 (m, 2H), 7.48-7.32 (m, 4H),
6.56 (s, 1H), 2.06 (s, 3H), 1.91 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 201.8, 170.2,
134.2, 131.3, 130.4, 129.6, 129.0, 128.3, 127.2, 126.3, 125.4, 123.9, 79.5, 26.3, 20.8.
1
4.3.23. 2-Oxo-1-(thiophen-2-yl)propyl acetate (2w) [36]. Pale brown oil. H NMR
(400 MHz, CDCl3): δ 7.41-7.38 (m, 1H), 7.15 (d, J = 3.2 Hz, 1H), 7.05 (dd, J = 4.8,
3.6 Hz, 1H), 6.23 (s, 1H), 2.19 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 200.5, 170.1,
134.6, 128.4, 127.8, 127.3, 75.9, 26.0, 20.6.
4.3.24. 2-Oxoundecan-3-yl acetate (2x). Colorless oil. 1H NMR (400 MHz, CDCl3): δ
4.92-4.88 (m, 1H), 2.08 (s, 3H), 2.07 (s, 3H), 1.71-1.62 (m, 2H), 1.33-1.17 (m, 12H),
0.81 (t, J = 6.6 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 205.4, 170.6, 78.7, 31.8, 30.2,
29.3, 29.2, 29.1, 26.0, 25.1, 22.6, 20.6, 14.0. HRMS calcd for C13H24O3 [M+]:
+
228.1725, found 228.1729.
4.3.25. 3-Oxo-1-phenylbutan-2-yl acetate (2y) [36]. Colorless oil. 1H NMR (400 MHz,
CDCl3): δ 7.29 (t, J = 7.2 Hz, 2H), 7.26-7.18 (m, 3H), 5.22-5.18 (m, 1H), 3.13-3.07
(m, 1H), 3.02-2.95 (m, 1H), 2.07 (s, 3H), 2.06 (s, 3H). 13C NMR (100 MHz, CDCl3):
δ 205.2, 170.3, 135.9, 129.3, 128.6, 127.1, 79.1, 36.7, 26.8, 20.6.
1
4.3.26. 4-Oxo-1-phenylpentan-3-yl acetate (2z). Colorless oil. H NMR (400 MHz,
CDCl3): δ 7.30 (t, J = 7.4 Hz, 2H), 7.23-7.15 (m, 3H), 5.00-4.95 (m, 1H), 2.75-2.67
18

(m, 2H), 2.16 (s, 3H), 2.13 (s, 3H), 2.12-2.01 (m, 2H). 13C NMR (100 MHz, CDCl3):
δ 205.1, 170.5, 140.4, 128.6, 128.4, 126.4, 78.1, 31.9, 31.5, 26.1, 20.7. HRMS calcd
+
for C13H16O3 [M+]: 220.1099, found 220.1094.
4.3.27. 2-Oxo-4-phenylpentan-3-yl acetate (2a'). Colorless oil.1H NMR (400 MHz,
CDCl3): δ 7.31 (t, J = 7.4 Hz, 2H), 7.27-7.21 (m, 3H), 5.04 (d, J = 6.0 Hz, 1H),
3.30-3.24 (m, 1H), 2.11 (s, 3H), 1.89 (s, 3H), 1.35 (d, J = 6.8 Hz, 3H). 13C NMR (100
MHz, CDCl3): δ 205.5, 170.5, 141.3, 128.7, 127.8, 127.3, 82.4, 40.8, 27.9, 20.5, 15.9.
+
HRMS calcd for C13H16O3 [M+]: 220.1099, found 220.1097.
1
4.3.28. 1-Cyclohexyl-2-oxopropyl acetate (2b'). Colorless oil. H NMR (400 MHz,
CDCl3): δ 4.76 (d, J = 4.4 Hz, 1H), 2.07 (s, 6H), 1.85-1.75 (m, 1H), 1.73-1.64 (m, 2H),
1.62-1.48 (m, 3H), 1.24-1.06 (m, 5H). 13C NMR (100 MHz, CDCl3): δ 205.5, 170.7,
+
82.6, 39.0, 29.3, 27.3, 27.1, 26.1, 25.9, 25.8, 20.6. HRMS calcd for C11H18O3 [M+]:
198.1256, found 198.1259.
4.3.29. (E)-5,9-dimethyl-2-oxodeca-4,8-dien-3-yl acetate (2c'). Colorless oil. 1H NMR
(400 MHz, CDCl3): δ 5.71 (d, J = 10.0 Hz, 1H), 5.15 (d, J =10.0 Hz, 1H), 5.03 (t, J =
5.6 Hz, 1H), 2.16-2.10 (m, 9H), 1.85 (s, 3H), 1.69-1.66 (m, 4H), 1.60 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ 202.6, 170.4, 145.9, 132.2, 123.3, 116.6, 76.5, 39.6, 26.1,
+
25.9, 25.7, 20.7, 17.7, 17.3. HRMS calcd for C14H22O3 [M+]: 238.1569, found
238.1574.
1
4.3.30. (E)-4-Oxo-1-phenylpent-1-en-3-yl acetate (2d'). Pale yellow oil. H NMR
(400 MHz, CDCl3): δ 7.28 (d, J = 7.2 Hz, 2H), 7.24-7.14 (m, 3H), 6.71 (d, J = 16.0
Hz, 1H), 6.06 (dd, J = 15.6, 8.0 Hz, 1H), 5.50 (dd, J = 7.6, 0.8 Hz, 1H), 2.10 (s, 3H),
19

2.06 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 202.3, 170.0, 136.2, 135.5, 128.8, 128.7,
+
126.8, 120.5, 79.9, 26.1, 20.7. HRMS calcd for C13H14O3 [M+]: 218.0943, found
218.0945.
4.3.31. 3,5-Dimethyl-2-oxohexan-3-yl acetate (2e') [36]. Colorless oil. 1H NMR (400
MHz, CDCl3): δ 2.12 (s, 3H), 2.08 (s, 3H), 1.80-1.72 (m, 2H), 1.69-1.63 (m, 1H), 1.52
(s, 3H), 0.95 (dd, J = 6.0, 3.6 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ 206.8, 170.1,
86.5, 44.4, 24.4, 24.0, 23.9, 23.7, 21.2, 20.5.
4.3.32. 2-(4-Bromophenyl)-3-oxobutan-2-yl acetate (2f'). Pale yellow oil. 1H NMR
(400 MHz, CDCl3): δ 7.51 (d, J = 8.8 Hz, 2H), 7.34 (d, J = 8.8 Hz, 2H), 2.26 (s, 3H),
1.95 (s, 3H), 1.82 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 203.2, 169.9, 137.7, 131.9,
+
126.6, 122.4, 87.1, 23.6, 22.8, 21.3. HRMS calcd for C12H13BrO3 [M+]: 284.0048,
found 284.0047.
1
4.3.33. 2-(3,4-Dimethylphenyl)-3-oxobutan-2-yl acetate (2g'). Pale yellow oil. H
NMR (400 MHz, CDCl3): δ 7.20-7.15 (m, 2H), 7.13 (d, J = 8.0 Hz, 1H), 2.27 (s, 3H),
2.25 (s, 6H), 1.95 (s, 3H), 1.82 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 203.8, 170.1,
137.0, 136.7, 136.0, 130.0, 125.9, 122.2, 87.5, 23.6, 22.9, 21.4, 20.0, 19.4. HRMS
+
calcd for C14H18O3 [M+]: 234.1256, found 234.1258.
1
4.3.34. 1-Acetylcyclohexyl acetate (2h') [36]. Colorless oil. H NMR (400 MHz,
CDCl3): δ 2.14-1.81 (m, 8H), 1.73-1.28 (m, 7H), 1.22-1.17 (m, 1H). 13C NMR (100
MHz, CDCl3): δ 207.1, 170.2, 85.2, 30.8, 25.0, 23.5, 21.1, 20.9.
Acknowledgements
20

We thank the National Natural Science Foundation of China (No. 21462021) and
Key Laboratory of Functional Small Organic Molecule, Ministry of Education (No.
KLFS-KF-201704) for financial support.
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23

Table 1 Optimization of the reaction conditions.a
Entry Gold catalyst (mol%)
Solvent
dioxane
dioxane
dioxane
dioxane
dioxane
CH2Cl2
MeOH
DMF
Time (h)
24
Yield (%)b
1
2
Ph2P-MCM-41-AuOTf (2)
Ph2P-MCM-41-AuNTf2 (2)
Ph2P-MCM-41-AuSbF6 (2)
Ph2P-MCM-41-AuBF4 (2)
Ph2P-MCM-41-AuCl (2)
Ph2P-MCM-41-AuSbF6 (2)
Ph2P-MCM-41-AuSbF6 (2)
Ph2P-MCM-41-AuSbF6 (2)
Ph2P-MCM-41-AuSbF6 (2)
Ph2P-MCM-41-AuSbF6 (1)
Ph2P-MCM-41-AuSbF6 (0.5)
Ph3PAuCl (1)/AgSbF6 (1)
85
74
97
80
0
24
3
5
4
24
5
36
6
24
68
42
0
7
24
8
36
9
DMSO
dioxane
dioxane
dioxane
36
0
10
11
12
12
96
91
97
24
8
a
Reactions were carried out with 1a (1.0 mmol), H2O (3.0 mmol) in solvent (1.5 mL) at room
temperature under Ar. b Isolated yield.
24

Table 2 Heterogeneous gold(I)-catalyzed synthesis of α-acyloxy methyl ketones.a,b
OAc
O
OAc
O
OAc
OAc
O
OAc
Me
Me
MeO
Me
Me
t-Bu
Me
Me
O
O
Me
BnO
2a, 96%
2c, 92%
2d, 89%
2b, 94%
2e, 91%
MeO
OAc
OAc
OAc
OAc
OAc
Me
Me
Me
Me
Me
O
O
O
O
O
2f, 90%
MeO
Ph
Cl
Br
F
2g, 90%
2h, 92%
2i, 93%
2j, 88%
OAc
OAc
OAc
O
OMe
OAc
OAc
O
Cl
Cl
Me
F3C
TBSO
Me
Me
Me
Me
O
O
O
O
2k, 95%
OMe
2l, 94%
2m, 81%
2n, 95%
2o, 92%
OAc
OAc
Cl
Br
Cl
OAc
OAc
OAc
OAc
Me
Me
Me
Me
O
O
O
O
O
Cl
MeO
2q, 91%
2r, 92%
2p, 95%
2s, 88%
2t, 93%
OAc
NO2
OAc
OAc
OAc
OAc
Me
Me
Me
Me
Me
O
Ph
O
O
S
O
O
2y, 91%
2w, 76%
2x, 93%
2v, 93%
2u, 94%
OAc
Me
OAc
OAc
OAc
OAc
Me
Me
Me
Me
Me
Me
Ph
Ph
Me
O
Ph
O
O
O
Me
O
2z, 90%
2a', 84%
2b', 85%
2d', 89%
2c', 82%
AcO
Me
AcO
AcO
Me
Me
Me
Me
OAc
Me
Me
Me
Me
O
Me
O
O
Me
O
Br
2g', 90%
2e', 93%
2f', 92%
2h', 86%
a Reactions were conducted with 1 (1.0 mmol), H2O (3.0 mmol), Ph2P-MCM-41-AuSb6 (1 mol%)
in 1,4-dioxane (1.5 mL) at room temperature under Ar for 12 h. b Isolated yield.
25

Table 3 Recycle of the Ph2P-MCM-41-AuSbF6 catalyst.a
Entry
Au Catalyst
Fresh
Yield (%)b
Entry
Au Catalyst
Recycle 4
Recycle 5
Recycle 6
Recycle 7
Yield (%)b
1
2
3
4
96
96
95
94
5
6
7
8
95
95
94
93
Recycle 1
Recycle 2
Recycle 3
a
Reactions were conducted with 1a (1.0 mmol), H2O (3.0 mmol), Ph2P-MCM-41-AuSbF6 (1
mol%) in 1,4-dioxane (1.5 mL) at room temperature under Ar for 12 h. b Isolated yield.
Scheme 1. Heterogeneous gold(I)-catalyzed hydration of propargyl acetates.
26

Scheme 2. Synthesis of the Ph2P-MCM-41-AuX complexes.
Scheme 3. Proposed catalytic cycle.
27

Fig. 1. 31P NMR spectra of fresh gold catalyst (a) and the recycled gold catalyst (b)
in CDCl3.
28

Research Highlights
► The heterogeneous Ph2P-MCM-41-AuSbF6 complex was first prepared.
► This gold(I) catalyst showed the same catalytic activity as Ph3PAuCl/AgSbF6
system.
► The reaction generated a variety of α-acyloxy methyl ketones in high yields.
► The gold(I) catalyst can be recycled up to 8 times with almost consistent activity.
► Our catalytic system provides a new and practical route to α-acyloxy methyl
ketones.