One-pot synthesis of α-acyloxycarbonyl compounds via oxidative decarboxylation coupling reaction of α-oxo carboxylic acids with carbonyl compounds

Article abstract of DOI:10.1016/j.tet.2016.09.031

With tetrabutylammonium iodide (TBAI) as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant, a simple metal-free protocol has been developed for the synthesis of α-acyloxycarbonyl compounds from carbonyl compounds and α-oxo carboxylic acids via decarboxylative coupling reaction. The target products could be obtained in moderate to high yields.

Full text of DOI:10.1016/j.tet.2016.09.031

Accepted Manuscript
One-pot synthesis of α-acyloxycarbonyl compounds via oxidative decarboxylation
coupling reaction of α-oxo carboxylic acids with carbonyl compounds
Li-Ming Chang, Gao-Qing Yuan
PII:
S0040-4020(16)30947-4
10.1016/j.tet.2016.09.031
TET 28102
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 July 2016
Revised Date: 12 September 2016
Accepted Date: 18 September 2016
Please cite this article as: Chang L-M, Yuan G-Q, One-pot synthesis of α-acyloxycarbonyl compounds
via oxidative decarboxylation coupling reaction of α-oxo carboxylic acids with carbonyl compounds,
Tetrahedron (2016), doi: 10.1016/j.tet.2016.09.031.
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One-pot synthesis of α-acyloxycarbonyl
compounds via oxidative decarboxylation
coupling reaction of α-oxo carboxylic acids
with carbonyl compounds
Leave this area blank for abstract info.
Li-Ming Chang and Gao-Qing Yuan*
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical
Engineering, South China University of Technology, Guangzhou 510640, China.

2
Tetrahedron
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Tetrahedron
journal homepage: www.elsevier.com
One-pot synthesis of α-acyloxycarbonyl compounds via oxidative decarboxylation
coupling reaction of α-oxo carboxylic acids with carbonyl compounds
Li-Ming Chang and Gao-Qing Yuan
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of
Technology, Guangzhou 510640, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
With tetrabutylammonium iodide (TBAI) as the catalyst and tert-butyl hydroperoxide
(TBHP) as the oxidant, a simple metal-free protocol has been developed for the synthesis of α-
acyloxycarbonyl compounds from carbonyl compounds and α-oxo carboxylic acids via
decarboxylative coupling reaction. The target products could be obtained in moderate to high
yields.
Available online
Keywords:
2009 Elsevier Ltd. All rights reserved
.
α-Acyloxycarbonyl compounds
Decarboxylation
Iodide catalysis
TBHP oxidation
1. Introduction
oxidative coupling reaction of carbonyl compounds with heavy
metal catalysts.9 In order to overcome the drawback of traditional
methods, some new methods have been investigated. For
example, Tomkinson and co-workers reported the synthesis of α-
acyloxycarbonyl compounds from ketones and N-methyl-O-
benzoylhydroxylamine.10 In 2012, the Bencivenni’s group
disclosed a chiral primary amine catalyzed the reaction of α-
oxybenzoylation with benzoyl peroxide.11 In addition, an
trimerization of aldehydes to α-acyloxycarbonyl compounds was
reported.12 Recently, the combination of TBHP with TBAI for
the synthesis of α-acyloxycarbonyl compounds or the activation
of C–H bond has drawn much attention.13 Inspired by these
achievements, we attempted to use TBHP as the oxidant and
TBAI as the catalyst to achieve α-acyloxylation of α-oxo
carboxylic acids with ketones via decarboxylation coupling
The decarboxylative functionalization of carboxylic acids is
one of the most attractive transformations in organic synthesis
since carboxylic acids are commercially available, and are easily
prepared by means of widely recognized methods. Moreover,
activated derivatives of carboxylic acids have long served as
versatile connection points in derivatizations and in the
construction
of
carbon
frameworks.1
In
particular,
decarboxylative coupling reactions have become an interesting
topic in recent years.2 However, oxidative decarboxylation that
involves carbon-heteroatom bond forming reactions, particularly
C–O, C–S and C–N bond formation,3 has received less attention.
Most of decarboxylative coupling reactions need heavy metal
catalysts and high reaction temperature, such as copper-catalyzed
aerobic decarboxylative sulfonylation of cinnamic acids with
sodium sulfinates,4 Pd-catalyzed decarboxylative coupling for the
synthesis of heteroaromatic biaryls and silver-catalyzed reaction
of aromatic carboxylic acids with alkenes.5 The use of an excess
of the transition metal reagents might be problematic.
reaction. This approach shows
a
simple and efficient
decarboxylative functionalization of α-oxo carboxylic acids
without transition metal catalysts. From the viewpoint of
synthetic methodology, the present work provides a new route for
the synthesis of α-acyloxycarbonyl compounds from ketones and
α-oxo carboxylic acids although α-oxo carboxylic acid as a
starting material is relatively precious.
The α-acyloxycarbonyl compound represents a significant
building block in organic synthesis,6 and exits in a substantial
number of both naturally occurring and synthetic biologically
significant molecules.7 Various synthetic approaches toward α-
acyloxycarbonyl compounds were developed in the past few
2. Result and Discussion
8
12
–
2.1. Optimization of reaction conditions
decades.
Traditional method is mainly based on the
substitution reaction of α-halo carbonyl compounds or the
———
Corresponding author. E-mail: gqyuan@scut.edu.cn (G. Yuan)

We initially employed
acid (1a) and
It should be noted that the product 3aa was not formed at
phenylglyoxylicACCEPTED MANUSCRIPT
propiophenone (2a) as model substrate to optimize the reaction
conditions, as shown in Table 1. According to our previous
experience, the reaction results are related to oxidants, catalysts
and solvents. The effect of oxidants was first examined. The
reaction proceeded in the presence of 20 mol% TBAI and 2
equivalents of ditertbutyl peroxide (DTBP) as an oxidant in
EtOAc (2 mL) at 80 °C for 24 hours (Table 1, entry 1). However,
the expected product 3a was not occurred. Similarly, other
oxidants, such as H2O2, K2S2O8 and I2, failed to achieve the
reaction (Table 1, entries 2–4). To our delight, the desired
product was obtained in a good yield (88%) when TBHP was
used as an oxidant (Table 1, entry 5). Moreover, the reaction
failed to implement in the absence of TBHP (Table 1, entry 6),
indicating that TBHP plays a crucial role in this transformation.
Catalyst was also a key factor. Replacing TBAI with KI to
catalyze the reaction, the α-acyloxylation product was obtained in
19% yield (Table 1, entry 7). Unfortunately, I2 and CuI did not
show any catalytic activity for this reaction (Table 1, entries 8
and 9). Meanwhile, the reaction did not happen in the absence of
TBAI (Table 1, entry 10). The experimental results indicated that
TBAI was particularly effective to catalyze this transformation.
Finally, in order to examine the effects of solvents, we screened a
variety of solvents. This reaction in PhCN or PhCl solvent
afforded the target product 3a in 67% and 59% yields,
respectively (Table 1, entries 11 and 12). Other solvents,
including THF, DMF, MeCN, and DMSO, were less efficient for
the reaction (Table 1, entries 13–16). By contrast, EtOAc as the
solvent appears to be more suitable to this reaction system (Table
1, entry 5).
80 °C or room temperature (Scheme 1, Eq. 1). Moreover, 3a
could be obtained in an acceptable yield (80%) when the reaction
was carried out on a 10.0 mmol scale (Scheme 1, Eq. 2),
indicating that this reaction is easily scalable.
Scheme 1.
2.2. Synthesis of α-acyloxycarbonyl compounds from α-oxo
carboxylic acids and ketones
With the optimized conditions in hand, the scope of α-oxo
carboxylic acids was examined, and the results were summarized
in Table 2. It could be seen that the reactions of propiophenone
with various good reactivity α-oxo carboxylic acids proceeded
smoothly to give the corresponding α-acyloxycarbonyl
compounds in high yields. The carboxylic acid substrates with
electron-withdrawing and electron-donating groups on the
aromatic rings all worked well to give the desired products (3a–
3f). However, possibly due to the effects of steric hindrance, the
yield of the target product decreased slightly when the aromatic
rings had ortho-position substituted groups (3g–3i).
Table 1
Optimization of reaction conditionsa
Table 2
Synthesis of α-acyloxycarbonyl compounds from α-oxo
carboxylic acids and propiophenone a
Entry Catalyst
(20 mol%)
Oxidant
(2 equiv)
Solvent
Yield (%) b
1
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
KI
DTBP
H2O2
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
PhCN
PhCl
0
2
0
3
K2S2O8
I2
0
4
0
5
TBHP
–
88
0
6
7
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
19
0
8
I2
9
CuI
0
10
11
12
13
14
15
16
–
0
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
67
59
7
a Reaction conditions as shown in Table 1. Isolated yields based on
phenylglyoxylic acid.
THF
Simultaneously, the scope of ketones for this transformation
was investigated. As shown in Table 3, propiophenone
derivatives substituted in para-position gave the desired products
(4a–4d) in good to excellent yields under the optimized
conditions. Notably, the substituents at the meta-position or
ortho-position seemed to decrease the reactivity slightly (4e–4g).
Pleasingly, cyclic ketones were also suitable to this reaction (4i
and 4l). Moreover, dimethylmalonate and benzoyl acetic ester
also worked well to afford the desired products (4j and 4k) with
good yields.
DMF
44
35
40
MeCN
DMSO
a Reaction conditions: 1a (0.2 mmol), 2a (0.2 mmol), solvent (2.0 mL) and at
80 °C for 24 h in a sealed tube.
b Yields were determined by GC–MS.

4
Tetrahedron
carbonyl radical 5 with tert-butyl perester 1aa gives the target
Table 3
ACCEPTED MANUSCRIPT
product 3 (path b), which may be a main pathway.
Synthesis
of
α-acyloxycarbonyl
compounds
from
phenylglyoxylic acid and ketonesa
a
Reaction conditions as shown in Table 1. Isolated yields based on
phenylglyoxylic acid.
Scheme 2. Control experiments.
2.3. Reaction mechanism
To gain insight into the reaction mechanism, a series of
control experiments were carried out (Scheme 2). The reaction
was completely inhibited in the presence of the radical scavenger
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), indicating that
this transformation may involve a radical pathway (Eq. 3). In the
absence of propiophenone 2a, phenylglyoxylic acid 1a was
almost converted into benzoic acid 3ab (Eq. 4). Simultaneously,
the target product 3a was isolated in 90% yield when benzoic
acid 3ab reacted with propiophenone under the standard
conditions (Eq. 5), which indicated that the benzoic acid might be
the key intermediate in the reaction system. In addition, replacing
propiophenone with 2-iodo-1-phenylpropan-1-one or 2-hydroxy-
1-phenylpropan-1-one, no reaction took place under the optimal
conditions (Eqs. 6 and 7). Therefore, it could be ruled out that the
possibility of 2-iodo-1-phenylpropan-1-one and 2-hydroxy-1-
phenylpropan-1-one as the reaction intermediates. Finally, tert-
butyl perester 1aa reacted with propiophenone 2a to afford 3a
with 86% yield in the absence of TBHP (Eq. 8), so we inferred
that tert-butyl perester 1aa might be the other intermediate in the
process of decarboxylative coupling transformation.
1/2 I2
+
tBuO
+
OH
I
+
tBuOOH
O
O
O
TBHP/ TBAI
TBHP/ TBAI
Ar
OOtBu
Ar
OH
3ab
Ar
COOH
1aa
1
OH
O
tBuO
Ar
O
7
O
R2
R1
Ar
O
path a
path b
O
3
1/2 I2
tBuO
O
O
O
R1
R1
R1
R2
R2
R2
tBuOH
2
5
6
I
Scheme 3. Proposed reaction mechanism.
3. Conclusion
Based on the control experiments and the related literatures, a
possible reaction mechanism is illustrated in Scheme 3. TBHP
firstly combines with TBAI to generate tert-butoxyl radicals and
iodine.13e,13i Then, the α-H of ketones is abstracted by tert-
butoxyl radicals to produce α-carbonyl radical 5,13c,13e followed
by the one-electron oxidation with iodine to form intermediate
cation 6.13c,13e In addition, the α-oxo carboxylic acid 1 undergoes
oxidative decarboxylation to form benzoic acid 3ab.13g,14 The
generated benzoic acid 3ab is deprotonated to give a benzoate
anion 7. The reaction of the intermediate cation 6 with the
benzoate anion 7 results in the final product 3 (path a). On the
other pathway, tert-butyl perester 1aa is easily formed in the
TBHP/TBAI system.13c,13j The coupling reaction of the α-
We have developed a novel TBAI-catalyzed method for the
oxidative decarboxylation coupling reaction of α-oxo carboxylic
acids with ketones, in which the C–C bond cleavage of α-oxo
carboxylic acids is due to TBHP oxidation. This transformation
undergoes a radical pathway. This metal-free catalytic system
provides a mild and efficient approach toward the synthesis of α-
acyloxycarbonyl compounds.
4. Experimental section
4.1. Instrumentation
All reagents and solvents were purchased from commercial
1
suppliers and used without further purification. H and 13C NMR
spectra were measured on a Bruker Advance 400 spectrometer

(400 MHz for 1H NMR, 100 MHz for 13C NMR spectroscopy) in
4.3.7.
1-Oxo-1-phenylpropan-2-yl 2-methylbenzoate (3g).13d
1
ACCEPTED MANUSCRIPT
White solid, mp 51–52 °C. H NMR (400 MHz, CDCl3) δ 8.00
(t, J=6.8 Hz, 3H), 7.56 (t, J=7.3 Hz, 1H), 7.46 (t, J=7.5 Hz, 2H),
7.38 (t, J=7.5 Hz, 1H), 7.23 (t, J=8.3 Hz, 2H), 6.19 (q, J=6.9 Hz,
1H), 2.58 (s, 3H), 1.64 (d, J=7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 196.8, 166.8, 140.4, 134.4, 133.5, 132.2, 131.5, 130.8,
128.9, 128.7, 128.4, 125.6, 71.7, 21.5, 17.1.
CDCl3. MS analyses were performed on a shimadzu GCMS-
QP5050A spectrometer. The new compounds were characterized
by a high resolution mass spectrometer (MAT95XP). TLC was
performed using commercially prepared 100–400 mesh silica gel
plates (GF254), and visualization was effected at 254 nm.
Melting points were determined with a Buchi B-545 melting
point instrument. Fourier transform infrared spectrum (FTIR)
was measured by a TENSOR27 spectrometer.
4.3.8.
1-Oxo-1-phenylpropan-2-yl 2-methoxybenzoate (3h).13d
1
White solid, mp 50–52 °C. H NMR (400 MHz, CDCl3) δ 8.00
(d, J=7.9 Hz, 2H), 7.91 (d, J=7.7 Hz, 1H), 7.56 (t, J=7.3 Hz, 1H),
7.45 (t, J=7.6 Hz, 3H), 6.96 (t, J=8.9 Hz, 2H), 6.19 (q, J=6.9 Hz,
1H), 3.84 (s, 3H), 1.63 (d, J=7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 196.9, 165.0, 159.4, 134.5, 133.8, 133.3, 131.8, 128.6,
128.4, 120.0, 118.9, 111.9, 71.4, 55.8, 16.9.
4.2. A typical procedure for the synthesis of α-
acyloxycarbonyl compounds
The mixture of phenylglyoxylic acid (0.2 mmol),
propiophenone (0.2 mmol), TBHP (0.4 mmol), TBAI (0.04 mmol)
and ethyl acetate (2 mL) was stirred at 80 °C for 24 h in a 15 mL
sealed tube successively. After cooling down, the reaction
mixture was washed with Na2S2O3 solution, and extracted by
ethyl acetate for three times. The obtained top organic layer was
dried with anhydrous MgSO4. After drying, the mixture was
concentrated under vacuum, and the crude product was purified
by column chromatography on silica gel with petroleum ether-
ethyl acetate (50:1) as eluent.
4.3.9.
1-Oxo-1-phenylpropan-2-yl 2,6-dichlorobenzoate (3i).
Pale yellow oil; IR (KBr) 3465–2938, 1749, 1692, 1271, 1226,
1143, 1080, 798 cm-1; H NMR (400 MHz, CDCl3) δ 8.02 (d,
1
J=7.5 Hz, 2H), 7.60 (t, J=7.4 Hz, 1H), 7.49 (t, J=7.4 Hz, 2H),
7.30–7.24 (m, 3H), 6.35 (q, J=6.8 Hz, 1H), 1.69 (d, J=6.9 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 195.4, 163.8, 134.2, 133.6,
132.5, 132.0, 131.1, 128.7, 128.6, 127.8, 72.6, 16.7; HRMS (ESI)
calcd for C16H12Cl2NaO3, [M+Na]+ 345.0056, found 345.0065.
4.3.10. 1-(4-Fluorophenyl)-1-oxopropan-2-yl benzoate (4a).13d
White solid, mp 81–82 °C. H NMR (400 MHz, CDCl3) δ 8.12–
1
8.04 (m, 4H), 7.60 (t, J=7.3 Hz, 1H), 7.47 (t, J=7.5 Hz, 2H), 7.18
(t, J=8.1 Hz, 2H), 6.17 (q, J=6.9 Hz, 1H), 1.69 (d, J=6.8 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 195.2, 167.2, 166.0, 164.7, 133.3,
131.3, 131.2, 130.9, 130.8, 129.8, 129.4, 128.4, 116.1, 115.9,
71.7, 17.1.
4.3.1.
1-Oxo-1-phenylpropan-2-yl
benzoate
(3a).13d
White solid, mp 101–103 °C. 1H NMR (400 MHz, CDCl3) δ 8.09
(d, J=7.8 Hz, 2H), 8.00 (d, J=7.8 Hz, 2H), 7.56 (t, J=6.9 Hz, 2H),
7.45 (m, 4H), 6.20 (q, J=6.8 Hz, 1H), 1.66 (d, J=6.9 Hz, 3H); 13
NMR (100 MHz, CDCl3): δ 196.7, 165.9, 134.4, 133.5, 133.2,
129.8, 129.5, 128.7, 128.4, 128.3, 71.8, 17.1.
C
4.3.11. 1-(4-Chlorophenyl)-1-oxopropan-2-yl benzoate (4b).13d
1
White solid, mp 93–94 °C. H NMR (400 MHz, CDCl3) δ 8.10
4.3.2.
1-Oxo-1-phenylpropan-2-yl 4-chlorobenzoate (3b).13d
(d, J=7.9 Hz, 2H), 7.96 (d, J=7.6 Hz, 2H), 7.59 (t, J=7.4 Hz, 1H),
7.45 (t, J=7.1 Hz, 4H), 6.15 (q, J=6.9 Hz, 1H), 1.67 (d, J=6.9 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 195.6, 165.9, 140.0, 133.3,
132.7, 129.9, 129.8, 129.3, 129.1, 128.4, 71.7, 17.0.
White solid, mp 101–102 °C. 1H NMR (400 MHz, CDCl3) δ 8.00
(q, J=8.0 Hz, 4H), 7.57 (t, J=7.4 Hz, 1H), 7.47 (t, J=7.5 Hz, 2H),
7.40 (d, J=7.6 Hz, 2H), 6.19 (q, J=6.8 Hz, 1H), 1.66 (d, J=7.0
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 196.4, 165.0, 139.6,
4.3.12. 1-(4-Bromophenyl)-1-oxopropan-2-yl benzoate (4c).13d
134.2, 133.6, 131.2, 128.7, 128.6, 128.4, 127.9, 72.0, 17.1
.
1
Pale yellow solid, mp 90–92 °C. H NMR (400 MHz, CDCl3) δ
4.3.3.
1-Oxo-1-phenylpropan-2-yl 4-bromobenzoate (3c).13d
8.07 (d, J=7.9 Hz, 2H), 7.86 (d, J=7.6 Hz, 2H), 7.67–7.55 (m,
3H), 7.45 (t, J=7.5 Hz, 2H), 6.12 (q, J=6.9 Hz, 1H), 1.66 (d, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 195.9, 165.9, 133.4,
133.2, 132.1, 130.0, 129.8, 129.3, 128.8, 128.4, 71.8, 17.0.
1
White solid, mp 118–119 °C. H NMR (400 MHz, CDCl3) δ
7.96 (q, J=7.8 Hz, 4H), 7.56 (d, J=7.4 Hz, 3H), 7.46 (t, J=7.5 Hz,
2H), 6.19 (q, J=6.9 Hz, 1H), 1.65 (d, J=6.9 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 196.3, 165.1, 134.2, 133.6, 131.6, 131.3,
129.7, 128.7, 128.4, 128.3, 72.0, 17.1.
4.3.13. 1-Oxo-1-(p-tolyl)propan-2-yl benzoate (4d).13e White
1
solid, mp 90–91 °C. H NMR (400 MHz, CDCl3) δ 8.12 (d,
4.3.4.
1-Oxo-1-phenylpropan-2-yl 4-methylbenzoate (3d).13d
J=7.8 Hz, 2H), 7.93 (d, J=7.7 Hz, 2H), 7.59 (t, J=7.4 Hz, 1H),
7.46 (t, J=7.5 Hz, 2H), 7.30 (d, J=7.8 Hz, 2H), 6.22 (q, J=6.9 Hz,
1H), 2.43 (s, 3H), 1.69 (d, J=6.9 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 196.2, 165.9, 144.5, 133.2, 131.9, 129.8, 129.6, 129.5,
128.6, 128.3, 71.8, 21.7, 17.3.
1
White solid, mp 85–86 °C. H NMR (400 MHz, CDCl3) δ 7.98
(t, J=6.5 Hz, 4H), 7.55 (t, J=7.3 Hz, 1H), 7.45 (t, J=7.4 Hz, 2H),
7.21 (d, J=7.7 Hz, 2H), 6.17 (q, J=6.9 Hz, 1H), 2.37 (s, 3H), 1.64
(d, J=6.9 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 196.7, 165.9,
143.9, 134.4, 133.4, 129.8, 129.0, 128.6, 128.4, 126.6, 71.6, 21.5,
17.0.
4.3.14. 1-(3-Fluorophenyl)-1-oxopropan-2-yl benzoate (4e).
White solid, mp 100–103 °C; IR (KBr) 3073–2938, 1727, 1690,
4.3.5.
1-Oxo-1-phenylpropan-2-yl 4-methoxybenzoate (3e).13d
1
1588, 1259, 1118, 714 cm-1; H NMR (400 MHz, CDCl3) δ 8.10
1
White solid, mp 102–103 °C. H NMR (400 MHz, CDCl3) δ
8.01 (q, J=8.0 Hz, 4H), 7.55 (t, J=7.3 Hz, 1H), 7.45 (t, J=7.5 Hz,
2H), 6.90 (d, J=8.7 Hz, 2H), 6.16 (q, J=6.9 Hz, 1H), 3.80 (s, 3H),
1.64 (d, J=7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 196.8,
165.5, 163.5, 134.4, 133.4, 131.8, 128.6, 128.3, 121.7, 113.5,
71.5, 55.2, 17.0.
(d, J=7.4 Hz, 2H), 7.80 (d, J=7.7 Hz, 1H), 7.71 (d, J=9.2 Hz,
1H), 7.60 (t, J=7.4 Hz, 1H), 7.47 (t, J=6.9 Hz, 3H), 7.31 (q,
J=10.0 Hz, 1H), 6.14 (q, J=6.8 Hz, 1H), 1.69 (d, J=6.9 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 195.7, 166.0, 164.1, 161.6, 161.2,
136.5, 136.5, 133.4, 130.5, 130.4, 129.9, 129.3, 128.4, 124.2,
124.2, 120.7, 120.5, 115.5, 115.2, 71.9, 17.0; HRMS (ESI) calcd
for C16H13FNaO3, [M+Na]+ 295.0741, found 295.0748.
4.3.6.
1-Oxo-1-phenylpropan-2-yl 3-methylbenzoate (3f).13d
1
White solid, mp 65–66 °C. H NMR (400 MHz, CDCl3) δ 7.99
(d, J=8.0 Hz, 2H), 7.89 (d, J=9.1 Hz, 2H), 7.55 (t, J=7.3 Hz, 1H),
7.45 (t, J=7.5 Hz, 2H), 7.36–7.28 (m, 2H), 6.19 (q, J=6.9 Hz,
1H), 2.36 (s, 3H), 1.65 (d, J=7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 196.6, 166.0, 138.0, 134.4, 133.9, 133.4, 130.2, 129.3,
128.7, 128.4, 128.2, 126.9, 71.7, 21.1, 17.0.
4.3.15. 1-(3-Nitrophenyl)-1-oxopropan-2-yl benzoate (4f).
Yellow oil; IR (KBr) 3390–2854, 1714, 1602, 1529, 1267, 1112,
1
713 cm-1; H NMR (400 MHz, CDCl3) δ 8.86 (s, 1H), 8.45 (d,
J=8.2 Hz, 1H), 8.32 (d, J=7.7 Hz, 1H), 8.08 (d, J=7.8 Hz, 2H),
7.71 (t, J=7.9 Hz, 1H), 7.60 (t, J=7.4 Hz, 1H), 7.46 (t, J=7.4 Hz,

6
Tetrahedron
ACCEPTED MANUSCRIPT
2H), 6.13 (q, J=6.9 Hz, 1H), 1.72 (d, J=6.9 Hz, 3H); 13C NMR
Duan, C. Tetrahedron. 2016, 72, 3858–3862; (h) Xu, W.; Huang, B.;
Dai, J.; Xu, J.; Xu, H. Org. Lett. 2016, 18, 3114–3117.
3. (a) Jia, W.; Jiao, N. Org. Lett. 2010, 12, 2000–2003; (b) Feng, H.; Song,
G.; Eycken, E. Org. Lett. 2012, 14, 1942–1945; (c) Bhadra, S.; Dzik, W.;
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4586–4589.
(100 MHz, CDCl3) δ 195.1, 166.0, 135.8, 134.0, 133.6, 130.1,
129.9, 129.7, 129.0, 128.5, 127.8, 123.4, 72.1, 16.9; HRMS (ESI)
calcd for C16H13NNaO5, [M+Na]+ 322.0686, found 322.0686.
4.3.16. 1-(2-Fluorophenyl)-1-oxopropan-2-yl benzoate (4g).
Pale yellow oil; IR (KBr) 3074–2939, 1727, 1697, 1609, 1269,
1112, 711 cm-1; 1H NMR (400 MHz, CDCl3) δ 8.09 (d, J=7.7 Hz,
2H), 7.95 (t, J=7.5 Hz, 1H), 7.58 (q, J=7.5 Hz, 2H), 7.46 (t, J=
7.5 Hz, 2H), 7.29 (t, J=7.5 Hz, 1H), 7.21–7.14 (m, 1H), 6.07 (q, J
=6.9 Hz, 1H), 1.68 (d, J=6.9 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 195.2, 165.9, 162.7, 135.1, 133.2, 131.2, 129.8, 129.6,
128.3, 124.8, 116.7, 116.5, 75.0, 16.1; HRMS (ESI) calcd for
C16H13FNaO3, [M+Na]+ 295.0741, found 295.0748.
4. Jiang, Q.; Xu, B.; Jia, J.; Zhao, A.; Zhao, Y.; Li, Y.; He, N.; Guo, C. J.
Org. Chem. 2014, 79, 7372–7379.
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6.
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4.3.17. 1-Oxo-1-phenylbutan-2-yl benzoate (4h).13d White
solid, mp 60–61 °C. H NMR (400 MHz, CDCl3) δ 8.11 (d,
Bornscheuer, U.; Wessjohann, L. Eur. J. Org. Chem. 2004, 1063–1074;
(d) Reddi, R.; Prasad, P.; Sudalai, A. Org. Lett. 2014, 16, 5674–5677.
1
J=7.7 Hz, 2H), 8.00 (d, J=7.7 Hz, 2H), 7.60–7.53 (m, 2H), 7.50–
7.40 (m, 4H), 6.06 (t, J=5.6 Hz, 1H), 2.13–1.99 (m, 2H), 1.11 (t,
J=7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 196.3, 166.1,
134.9, 133.5, 133.2, 129.8, 129.6, 128.7, 128.4, 128.3, 76.7, 24.9,
9.9.
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3252.
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J.; Jin, Y.; Choi, J. Chem. Commun. 2001, 956–957; (c) Cadierno, V.;
Francos, J.; Gimeno, J. Green Chem. 2010, 12, 135–143; (d) Reid, B.;
Barchi, J.; Faghih, J. J. Org. Chem. 1988, 53, 925–926; (e) Cadierno, V.;
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4.3.18. 2-Oxocyclohexyl benzoate (4i).13d White solid, mp 85–
1
86 °C. H NMR (400 MHz, CDCl3) δ 8.09 (d, J=7.4 Hz, 2H),
7.57 (t, J=7.4 Hz, 1H), 7.45 (t, J=7.5 Hz, 2H), 5.41 (q, J=9.0 Hz,
1H), 2.57 (d, J=12.7 Hz, 1H), 2.51–2.41 (m, 2H), 2.15–2.11 (m,
1H), 2.04 (d, J=13.2 Hz, 1H), 1.96–1.83 (m, 2H), 1.65 (q, J=13.6
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 204.3, 165.6, 133.1,
129.9, 129.7, 128.3, 76.7, 40.7,33.2, 27.2, 23.8.
4.3.19. 1-Ethoxy-1,3-dioxo-3-phenylpropan-2-yl
benzoate
(4j).13d Pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.11 (t, J=
9.2 Hz, 4H), 7.67–7.60 (m, 2H), 7.55–7.45 (m, 4H), 6.55 (s, 1H),
4.31 (q, J=7.0 Hz, 2H), 1.26 (t, J=6.9 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 189.8, 165.2, 165.1, 134.3, 134.2, 133.8, 130.1,
129.3, 128.8, 128.5, 128.4, 74.9, 62.5, 13.9.
4.3.20. Dimethyl 2-(benzoyloxy)malonate (4k).13a Pale yellow
1
oil. H NMR (400 MHz, CDCl3) δ 8.14 (d, J=7.9 Hz, 2H), 7.61
(t, J=7.2 Hz, 1H), 7.48 (t, J=7.5 Hz, 2H), 5.81 (s, 1H), 3.87 (s,
6H); 13C NMR (100 MHz, CDCl3) δ 165.1, 164.9, 133.9, 130.2,
128.5, 128.3, 71.8, 53.3.
1
4.3.21. 2-Oxocycloheptyl benzoate (4l).10 Pale yellow oil. H
NMR (400 MHz, CDCl3) δ 8.08 (d, J=7.8 Hz, 2H), 7.57 (t, J =7.3
Hz, 1H), 7.45 (t, J=7.4 Hz, 2H), 5.46 (t, J=7.6 Hz, 1H), 2.74 –
2.66 (m, 1H), 2.55–2.47 (m, 1H), 2.16–2.09 (m, 1H), 1.92–1.64
(m, 6H), 1.49–1.41 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
207.4, 165.8, 133.2, 129.8, 129.7, 128.4, 79.0, 40.7, 30.4, 28.4,
26.4, 23.0.
14. Lippert, A.; Keshari, K.; Kurhanewicz, J.; Chang, C. J. Am. Chem. Soc.
2011, 133, 3776–3779.
Supplementary Material
Supplementary material that may be helpful in the review
process should be prepared and provided as a separate electronic
file. That file can then be transformed into PDF format and
submitted along with the manuscript and graphic files to the
appropriate editorial office.
Acknowledgments
We are grateful to the National Natural Science Foundation of
China (21572070 and 21172079) for the financial support.
References and notes
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