One approach to cyclic carbonates via a three-component cyclization of phenacyl bromide, CO2, and aldehyde

Article abstract of DOI:10.1021/jo1020294

A three-component cyclization reaction was designed for synthesizing cyclic carbonates in a single operation from phenacyl bromide, CO₂, and aldehyde in the presence of lithium diisopropylamide (LDA). These novel reactions were achieved under extremely mild conditions to generate the target products in moderate to good yields within 10 min.

Full text of DOI:10.1021/jo1020294

ARTICLE
pubs.acs.org/joc
One Approach to Cyclic Carbonates via a Three-Component
Cyclization of Phenacyl Bromide, CO , and Aldehyde
2
Peng Yan, Xueqin Tan, Huanwang Jing,* Shuhui Duan, Xiaoxuan Wang, and Zhongli Liu
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University,
Lanzhou 730000, Gansu, People's Republic of China
S Supporting Information
b
ABSTRACT: A three-component cyclization reaction was de-
signed for synthesizing cyclic carbonates in a single operation
from phenacyl bromide, CO , and aldehyde in the presence of
2
lithium diisopropylamide (LDA). These novel reactions were
achieved under extremely mild conditions to generate the target
products in moderate to good yields within 10 min.
’
INTRODUCTION
anionic intermediate in the mechanism of the Darzens reaction and
6d,11
the mechanism of cyclic carbonate synthesis,
we have designed a
The chemistry of CO has received much attention from the
2
three-component cyclization reaction for cyclic carbonate synthesis in
viewpoint of carbon resources and environmental problems in the
past decade. Cyclic carbonates, as one of the products of CO2
chemistry, are attractive and important compounds in a variety of
chemical research fields, such as polar aprotic solvents and inter-
1
an one-pot reaction from phenacyl bromide, CO , and aldehyde using
2
LDA as a base. This new strategy for cyclic carbonate synthesis avoids
the rigorous reaction conditions of high pressure, high temperature,
and long reaction time, generating trans cyclic carbonates from
2
mediates in organic synthesis that can be used for the protection of
3
phenacyl bromide, CO , and aldehyde.
2
1,2- and 1,3-diols and the construction of structurally complex
4
molecules. Biologically active molecules that contain a cyclic
carbonate component have also been isolated from various kinds
of natural sources. Cyclic carbonates can be normally synthesized
5
’
RESULTS AND DISCUSSION
by a cycloaddition reaction of CO with epoxides in the presence of
various activating reagents. Although numerous synthetic methods
for the syntheses of carbonates have been documented in the
literature, they have the limitation of depending upon the initial
epoxide substrate.
2
We set out to access the scope and limitations of the reactions
6
using phenacyl bromide, CO , and benzaldehyde as the model
2
substrate in the presence of strong bases such as n-BuLi, KO-tert-Bu,
LDA, Cs CO , etc. After we screened the bases, LDA was found to
2
3
be the best choice to initiate this reaction. Then, solvent effects were
investigated. The results given in Table 1 demonstrated that 1,4-
dioxane is the best medium for cyclic carbonate formation (entry 2).
The yield of cyclic carbonate slightly decreased in tetrahydrofuran
(THF) (entry 1). Reactions in other dry solvents, including
dimethyl sulfoxide (DMSO) and dimethylformamide (DMF), were
less suitable and gave extremely low yields (entries 3-6). In
contrast, these solvents give higher yields of epoxide (entries 5
and 6). These observations could be explained in terms of the effect
of the polarity of solvent: the less the polarity of the solvent, the
more cyclic carbonate produced. This is attributed to the higher
nucleophilicity of an oxygen anion in a less polar solvent.
Recently, He et al. reported an environmentally benign synthesis of
styrene carbonate directly from styrene and CO catalyzed by a binary
2
system composed of sodium phosphotungstate and n-Bu NBr using
4
7
3
0% H O as an oxidant. We have recently disclosed that dioxo-
2 2
(
tetraphenylporphyrinato)ruthenium(VI) and quaternary onium
salts can be used as effective catalysts to initiate a three-component
reaction of olefin, O , and CO at ambient temperature under low
2
2
8
pressure for producing cyclic carbonates. Although these findings
furnish a simple and more cost-effective pathway for the environmen-
tally benign chemical fixation of CO to produce cyclic carbonates,
2
the method requires harsh reaction conditions such as relatively high
pressure, high temperature, and long reaction time, using toxic or
costly reagents and requiring a tedious workup for separation despite
The temperature effect was then investigated in pursuit of the
optimum reaction conditions (Table 2). The yield of cyclic
carbonate increased when the temperature was raised from 15
to 35 °C (entries 1-3). The best yield of 68% was obtained at
6c,d,9
a few efficient methods exploited up to now.
For extending the
applications of cyclic carbonates, it is desirable to develop new
methodology that can operate under mild conditions. We take note
3
5 °C. However, the yield of target product decreased when the
10
of the Darzens reaction, which is traditionally carried out in the
presence of strong base and mechanistically includes an aldol reaction
of an R-halo carbonyl compound with an aldehyde to form a C-C
bond followed by an intramolecular cyclization of the intermediate
halohydrin compound to form an epoxide. Considering the same
temperature was over 35 °C (entry 4). In contrast, the reaction
ceased at 0 °C (entry 5).
Received: October 12, 2010
Published: March 14, 2011
r 2011 American Chemical Society
2459
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The Journal of Organic Chemistry
ARTICLE
a
Table 1. Effect of Solvent on the Cyclic Carbonate Synthesis
c
yield (%)
b
entry
solvent
THF
conv (%)
1a
1b
1
2
3
4
5
6
90
92
42
35
62
58
62
68
21
17
5
21
18
16
14
42
47
1,4-dioxane
n-butyl ether
acetonitrile
DMSO
DMF
4
a
Reactions were carried out at 35 °C with 2 mmol of benzaldehyde and 4 mmol of phenacyl bromide, under an atmosphere of CO (1 atm) over 10 min
2
b
c
after LDA addition. Conversion based on the benzaldehyde. Isolated yield after column chromatography.
a
Table 2. Effect of Temperature on the Yield of Polysubstituted Cyclic Carbonate
c
yield (%)
b
entry
temp (°C)
conv (%)
1a
1b
1
2
3
4
5
15
25
35
45
0
42
58
92
94
0
28
38
68
61
0
8
11
18
25
0
a
2
Reactions were carried out with 2 mmol of benzaldehyde and 4 mmol of phenacyl bromide, under an atmosphere of CO (1 atm) over 10 min after
LDA addition. Conversion based on the benzaldehyde. Isolated yield after column chromatography.
b
c
To further extend the scope of the substrate, various substituted
aldehydes and substituted phenacyl bromides were introduced into
this three-component reaction, affording the corresponding cyclic
carbonates. The results are summarized in Table 3. Clearly, the
substituted groups with various electronic characters on the phenyl
ring of the aldehydes and phenacyl bromides influenced the reaction
activities and selectivities (entries 1-24). We note that the substrates
with an electron-donating group on the phenyl ring have a selectivity
toward formation of cyclic carbonates higher than for those bearing an
electron-withdrawing group (entries 2-7 vs entries 8-16). Treat-
reactivity and selectivity due to their higher cation charge and
stereochemical effects (entries 3, 6, 8, and 17-20). In contrast, the
fatty aldehydes gave low yield and selectivity (entries 25-29). It is
worth pointing out that cinnamaldehyde and 2-furaldehyde can
uniquely produce the corresponding cyclic carbonates (entries 30
and 31). On the other hand, when ethyl 2-bromoacetate was used
instad of phenacyl bromide, this type of reaction could not occur;
when 1-bromoacetone or 2-bromo-N-phenylacetamide was used
instad of phenacyl bromide, the relevant epoxide could be found in
the products, but the target product of cyclic carbonate could not be
found. Obviously, the phenyl ring of phenacyl bromides plays a key
factor in this reaction because it can stabilize the carbanion inter-
mediate, allowing the reaction to take place (vide infra).
ment of an aromatic aldehyde having a 2-CH group with phenacyl
3
bromide gave the corresponding product in 81% yield and 100%
selectivity (entry 6). However, the aldehyde with the NO group can
2
only be converted to the corresponding cyclic carbonate in both low
yield and selectivity (entries 14-16). Interestingly, the same groups
substituted at a different position on the phenyl ring of the aldehyde
also influence the reaction activities and selectivities (entries 2 and 3,
entries 4-6, entries 8-10, and entries 14-16). It can be seen that
the aromatic aldehydes with ortho-substituted groups show higher
On the basis of the experimental results described above, we
propose a plausible reaction mechanism (Scheme 1). The first
step of the mechanism is an aldol reaction: the LDA deprotonates
the phenacyl bromide, resulting in carbanion A. The carbon
anion of A then attacks the carbonyl group of the aldehyde,
yielding intermediate B. The oxygen anion of B then attacks the
2
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The Journal of Organic Chemistry
ARTICLE
a
Table 3. Effect of Substituent for the Yield of Cyclic Carbonate
a
Reactions were carried out at 35 °C with 2 mmol of aldehyde and 4 mmol of substituted phenacyl bromide, under an atmosphere of CO (1 atm) over
2
b
c
1
0 min after LDA addition. Conversion based on the benzaldehyde. Isolated yield after column chromatography.
carbon of CO to form the new intermediate C. Then, the
provides a new route to cyclic carbonates via aldehydes and
2
intramolecular cyclization of C via oxygen anion attack at the R-
a good example of utilizing CO as a building block in organic
2
carbon of the carbonyl led to formation of the product a
synthesis. The products also enrich the family of cyclic carbonates.
-
accompanied by the departure of Br . On the other hand, when
the oxygen anion of intermediate B directly attacks the R-carbon
of carbonyl, the byproduct b is produced under the reaction
conditions.
’
EXPERIMENTAL SECTION
General Procedure for the Preparation of Cyclic Carbonates.
In summary, we have discovered a new and concise method to
fabricate the trans cyclic carbonates via a three-component
Carbon dioxide was bubbled into the solution of phenacyl bromide
(0.8 g, 4 mmol) with various aldehydes (2 mmol) in anhydrous dioxane
(5 mL). Then LDA (2.5 mL, 1 M) was added dropwise by syringe to the
above solution at 35 °C over 2.5 min with vigorous stirring. The reaction
was allowed to proceed at 35 °C with constant bubbling of carbon
cyclization reaction of substituted phenacyl bromide, CO , and
2
various aldehydes in the presence of LDA under extremely mild
conditions in good yields within 10 min. This robust methodology
2
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ARTICLE
Scheme 1. Proposed Mechanism for Polysubstituted Cyclic
Carbonate Synthesis
4-(3,4-Dimethylphenyl)-5-benzoyl-1,3-dioxolan-2-one (7a).
H NMR (300 MHz, CDCl ): δ 7.90 (d, J = 7.5 Hz, 2H), 7.62 (t, J =
1
3
7
.5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 2H), 7.19-7.11 (m, 3H), 5.80 (d, J = 6.0
13
Hz, 1H), 5.61 (d, J = 5.7 Hz, 1H), 2.26 (s, 6H). C NMR (75 MHz,
CDCl ): δ 191.2, 153.2, 138.6, 137.8, 134.8, 133.2, 132.8, 130.4, 129.2,
3
1
C
28.9, 127.1, 123.5, 81.7, 79.1, 19.7, 19.5. HRMS (ESI): m/z calcd for
þ
18
H
4
16
O
4
[M þ NH
4
]
314.1387, found 314.1384.
-(2-Chlorophenyl)-5-benzoyl-1,3-dioxolan-2-one (8a).
H NMR (400 MHz, acetone-d ): δ 8.08 (d, J = 8.0 Hz, 2H), 7.73
t, J = 7.6 Hz, 1H), 7.67-7.65 (m, 1H), 7.57 (d, J = 8.0, 7.6 Hz, 2H),
.54-7.49 (m, 3H), 6.37 (d, J = 4.8 Hz, 1H), 6.30 (d, J = 5.2 Hz, 1H).
3
1
6
(
7
1
6
C NMR (100 MHz, acetone-d ): δ 192.7, 154.1, 135.6, 134.6, 134.4,
1
33.1, 132.1, 131.2, 130.2, 129.8, 129.2, 128.8, 80.4, 77.2. HRMS (ESI):
þ
m/z calcd for C16
H
11ClO
4
[M þ NH
4
]
320.0684, found 320.0681.
4
-(3-Chlorophenyl)-5-benzoyl-1,3-dioxolan-2-one (9a).
H NMR (300 MHz, CDCl ): δ 7.82 (d, J = 7.8 Hz, 2H), 7.52 (d, J = 7.8
Hz, 1H), 7.39-7.18 (m, 6H), 5.84 (d, J = 6.3 Hz, 1H), 5.49 (d, J = 6.6 Hz,
1
3
13
3
1H). C NMR (75 MHz, CDCl ): δ 190.9, 152.7, 137.3, 135.0, 134.9,
1
32.9, 130.5, 129.7, 129.2, 128.9, 125.9, 124.0, 81.4, 77.8. HRMS (ESI): m/z
þ
calcd for C16
H
11ClO
4
[M þ NH
4
]
320.0684, found 320.0677.
-(4-Chlorophenyl)-5-benzoyl-1,3-dioxolan-2-one (10a).
4
1
H NMR (400 MHz, CDCl ): δ 7.95 (d, J = 7.6 Hz, 2H), 7.70-7.67 (t,
3
J = 7.2, 7.6 Hz, 1H), 7.53 (t, J = 7.6 Hz, 2H), 7.45 (dd, J = 6.4 Hz, 2H),
7.38 (d, J = 8.4 Hz, 2H), 6.00 (d, J = 6.4 Hz, 1H), 5.53 (d, J = 6.4 Hz, 1H).
C NMR (100 MHz, CDCl ): δ 191.1, 152.7, 135.9, 135.1, 134.1,
3
dioxide and stirring for 10 min. The reaction mixture was quenched with
water and extracted with ethyl acetate (10 mL ꢀ 3), and the extracts
were dried over anhydrous magnesium sulfate. The solvent was evapo-
rated under vacuum. The crude residue was purified by column
chromatography (12/1 petroleum ether (60-90 °C)/EtOAc), afford-
ing the pure target product and byproduct. This procedure was followed
for all the reactions given in Table 3. The known compounds were
identified by comparison of their spectra with those of authentic
1
3
133.3, 129.6, 129.4, 129.1, 127.3, 81.9, 78.2. HRMS (ESI): m/z calcd for
þ
C
16
H
4
11ClO
4
[M þ NH
4
]
-(2,4-Dichlorophenyl)-5-benzoyl-1,3-dioxolan-2-one (11a).
320.0684, found 320.0687.
1
H NMR (300 MHz, CDCl ): δ 7.91 (d, J = 8.4 Hz, 2H), 7.59 (t, J =
3
7
.5 Hz, 1H), 7.46-7.31 (m, 4H), 7.29 (m, 1H), 6.27 (d, J = 4.5 Hz, 1H),
13
3
5.63 (d, J = 4.5 Hz, 1H). C NMR (75 MHz, CDCl ): δ 190.2, 152.8,
2b
136.2, 134.9, 133.1, 132.3, 132.1, 130.1, 129.3, 129.0, 128.4, 128.0, 79.6,
samples. The unknown compounds listed in Table 3 were properly
þ
1
13
75.4. HRMS (ESI): m/z calcd for C H Cl O [M þ NH ] 354.0294,
1
6
10
2
4
4
characterized by H and C NMR and HRMS:
-(2-Methoxyphenyl)-5-benzoyl-1,3-dioxolan-2-one (3a).
H NMR (300 MHz, CDCl ): δ 7.97 (d, J = 8.1 Hz, 2H), 7.67 (t, J = 7.5,
.2 Hz, 1H), 7.52 (t, J = 7.8, 7.5 Hz, 2H), 7.49-7.38 (m, 2H), 7.04 (t, J =
.8, 7.5 Hz, 1H), 6.95 (d, J = 8.1 Hz, 1H), 6.03 (d, J = 5.7 Hz, 1H), 5.71
found 354.0299.
4-(2-Bromophenyl)-5-benzoyl-1,3-dioxolan-2-one (12a).
4
1
3
1
H NMR (300 MHz, CDCl
H), 7.51-7.40 (m, 5H), 6.34 (d, J = 4.5 Hz, 1H), 5.72 (d, J = 4.2 Hz, 1H).
3
3
): δ 7.98 (d, J = 8.1 Hz, 2H), 7.64-7.57 (m,
7
7
2
1
13
C NMR (75 MHz, CDCl ): δ 190.4, 153.1, 135.1, 134.8, 133.4, 133.3,
3
(d, J = 5.7 Hz, 1H), 3.71 (s, 3H). C NMR (75 MHz, CDCl
3
): δ 191.7,
1
31.0, 129.3, 128.9, 128.2, 127.3, 120.7, 79.7, 77.4. HRMS (ESI): m/z calcd
1
7
3
56.5, 153.8, 134.6, 133.8, 131.0, 129.2, 128.9, 127.7, 123.9, 121.0, 110.9,
þ
for C16
H
11BrO
4
[M þ NH
4
]
364.0179, found 364.0175.
þ
4
9.7, 77.0, 55.3. HRMS (ESI): m/z calcd for C H O [M þ NH ]
17
14
5
4
-(4-Fluorophenyl)-5-benzoyl-1,3-dioxolan-2-one (13a).
H NMR (300 MHz, acetone-d ): δ 8.00 (m, J = 8.1 Hz, 2H), 7.75-7.64
m, 3H), 7.57 (t, J = 7.5, 7.8 Hz, 2H), 7.29 (t, J = 8.4 Hz, 8.7 Hz, 2H),
16.1179, found 316.1180.
1
6
4
-(4-Methylphenyl)-5-benzoyl-1,3-dioxolan-2-one (4a; 4-p-Tolyl-
(
1
1
,3-dioxolan-2-one). H NMR (300 MHz, CDCl ): δ 7.91 (d, J = 7.5
13
3
6
.24 (d, J = 6.0 Hz, 1H), 6.06 (d, J = 5.7 Hz, 1H). C NMR
Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H), 7.48 (t, J = 7.5 Hz, 2H), 7.31-7.23
(75 MHz, acetone-d
6
): δ 193.0, 165.9, 162.6, 154.1, 135.5, 134.7,
(
m, 4H), 5.85 (d, J = 5.7 Hz, 1H), 5.61 (d, J = 5.7 Hz, 1H), 2.37 (s, 3H).
1
33.3, 133.2, 130.3, 130.2, 130.1, 129.9, 117.1, 116.8, 82.2, 79.6. HRMS
1
3
C NMR (75 MHz, CDCl
3
): δ 191.2, 153.2, 140.0, 134.9, 133.2, 132.5,
þ
(
ESI): m/z calcd for C H FO [M þ NH4] 304.0980, found
1
6
11
4
1
C
29.9, 129.2, 129.0, 126.0, 81.8, 79.1, 21.2. HRMS (ESI): m/z calcd for
3
04.0978.
-(2-Nitrophenyl)-5-benzoyl-1,3-dioxolan-2-one (14a). H
NMR (300 MHz, CDCl ): δ 8.25 (d, J = 8.4 z, 1H), 8.04 (d, J = 8.0 Hz,
2H), 7.85 (d, J = 4.2 Hz, 2H), 7.70-7.63 (m, 2H), 7.53 (t, J = 7.8, 7.5 Hz,
þ
17
H
4
14
O
4
[M þ NH
4
]
300.1230, found 300.1235.
-(3-Methylphenyl)-5-benzoyl-1,3-dioxolan-2-one (5a; m-Tolyl-
1
4
3
1
1
,3-dioxolan-2-one). H NMR (400 MHz, acetone-d ): δ 8.00 (d,
6
J = 8.0 Hz, 2H), 7.71 (t, J = 7.6 Hz, 1H), 7.56 (t, J = 8.0, 7.6 Hz, 2H),
13
2
H), 6.71 (d, J = 3.9 Hz, 1H), 5.74 (d, J = 3.6 Hz, 1H). C NMR
7
5
.39-7.36 (m, 3H), 7.30 (d, J = 7.6 Hz, 1H), 6.20 (d, J = 5.6 Hz, 1H),
(
75 MHz, CDCl ): δ 190.1, 153.2, 145.8, 135.2, 134.8, 133.6, 133.4,
3
13
.96 (d, J = 5.6 Hz, 1H), 2.38 (s, 3H). C NMR (100 MHz, acetone-d ):
6
130.3, 129.4, 129.0, 126.8, 125.9, 79.4, 75.2. HRMS (ESI): m/z calcd for
þ
δ 193.0, 154.2, 139.8, 137.0, 135.4, 134.5, 131.3, 129.98, 129.95, 129.8,
C
16
H
4
11NO
6
[M þ NH
4
]
331.0925, found 331.0932.
1
1
28.1, 124.6, 82.1, 80.1, 21.4. HRMS (ESI): m/z calcd for C17
H
14
O
4
[M
-(3-Nitrophenyl)-5-benzoyl-1,3-dioxolan-2-one (15a). H
NMR (300 MHz, CDCl ): δ 8.37 (s, 1H), 8.30 (d, J = 8.1 Hz, 1H), 8.04
(d, J = 7.5 Hz, 2H), 7.88 (d, J = 8.1 Hz, 1H), 7.74-7.70 (m, 2H), 7.59-
þ
þ NH
4
]
300.1230, found 300.1224.
-(2-Methylphenyl)-5-benzoyl-1,3-dioxolan-2-one (6a; o-Tolyl-
3
4
1
13
1
2
,3-dioxolan-2-one). H NMR (300 MHz, CDCl
H), 7.63 (t, J = 7.8 Hz, 1H), 7.49-7.42 (m, 3H), 7.33-7.30 (m, 2H), 7.21-
.18 (m, 1H), 6.22 (d, J = 5.4 Hz, 1H), 5.66 (d, J = 6.0 Hz, 1H), 2.27 (s, 3H).
3
): δ 7.91 (d, J = 7.2 Hz,
7.53 (m, 2H), 6.23 (d, J = 6.3 Hz, 1H), 5.71 (dd, J = 1.8, 6.3 Hz, 1H). C
NMR (75 MHz, CDCl ): δ 190.9, 152.3, 148.4, 137.5, 135.1, 133.0,
3
7
132.0, 130.5, 129.4, 129.0, 124.4, 121.0, 81.6, 77.5. HRMS (ESI): m/z
1
3
þ
3
C NMR (75 MHz, CDCl ): δ 191.1, 153.2, 135.7, 134.8, 133.5, 133.1, 131.2,
calcd for C H NO [M þ NH ] 331.0925, found 331.0929.
1
6
11
6
4
1
1
29.6, 129.2, 128.9, 126.9, 125.7, 81.1, 76.1, 18.9. HRMS (ESI): m/z calcd for
4-(4-Nitrophenyl)-5-benzoyl-1,3-dioxolan-2-one (16a). H
þ
C H O [M þ NH ] 300.1230, found 300.1228.
NMR (300 MHz, CDCl ): δ 8.27 (dd, J = 1.8, 8.7 Hz, 2H), 7.98 (d, J =
1
7
14
4
4
3
2
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ARTICLE
1
8
6
.7 Hz, 2H), 7.64 (t, J = 9.0, 8.7 Hz, 3H), 7.51 (t, J = 8.4, 7.5 Hz, 2H),
.18 (d, J = 6.9 Hz, 1H), 5.53 (d, J = 6.6 Hz, 1H). C NMR (75 MHz,
4-Benzoyl-5-pentyl-1,3-dioxolan-2-one (25a). H NMR
13
(300 MHz, acetone-d ): δ 7.92 (d, J = 5.4 Hz, 2H), 7.62-7.57 (m,
6
CDCl
3
): δ 190.9, 152.3, 148.4, 142.4, 135.2, 133.1, 129.5, 129.1, 126.7,
1H), 7.49-7.44 (m, 2H), 5.81 (d, J = 4.8 Hz, 1H), 4.84-4.79 (m, 1H),
1.87-1.79 (m, 2H), 1.42-1.30 (m, 2H), 1.27-1.17 (m, 4H), 0.77-
þ
1
3
24.4, 81.6, 77.4. HRMS (ESI): m/z calcd for C16
31.0925, found 331.0928.
-Benzoyl-5-(2,5-dimethoxyphenyl)-1,3-dioxolan-2-one (17a).
H NMR (300 MHz, CDCl ):δ7.95 (d, J= 7.8 Hz, 2H), 7.65 (t, J=7.5, 6.9
H11NO
6
[M þ NH
4
]
1
3
0.73 (m, 3H). C NMR (75 MHz, CDCl ): δ 191.9, 153.3, 134.6, 133.4,
3
4
129.1, 128.9, 79.7, 78.4, 33.9, 31.0, 23.9, 22.2, 13.7. HRMS (ESI): m/z
1
þ
calcd for C15
H
18
O
4
[M þ NH
4
]
280.1543, found 280.1546.
3
1
Hz, 1H), 7.50 (t, J = 7.5, 7.2 Hz, 2H), 6.94-6.83 (m, 3H), 5.95 (d, J = 5.4
4-Benzoyl-5-hexyl-1,3-dioxolan-2-one (26a). H NMR (300
MHz, CDCl ): δ 7.99 (d, J = 8.4 Hz, 2H), 7.67 (t, J = 7.8, 6.3 Hz, 1H),
13
Hz, 1H), 5.71 (d, J = 5.4 Hz, 1H), 3.77 (s, 3H), 3.60 (s, 3H). C NMR (75
MHz, CDCl ): δ 191.6, 153.7, 153.6, 150.2, 134.6, 133.7, 129.0, 128.9,
24.7, 115.2, 113.2, 111.9, 79.6, 76.6, 55.8, 55.5. HRMS (ESI): m/zcalcd for
3
7.54 (t, J = 7.5, 7.8 Hz, 2H), 5.34 (d, J = 5.1 Hz, 1H), 5.00-4.95 (m, 1H),
3
1
1.93-1.80 (m, 2H), 1.54-1.29 (m, 8H), 0.89 (t, J = 6.3, 5.4 Hz, 3H).
þ
13
C
18
H
4
16
O
6
[M þ NH
-Benzoyl-5-(2-butoxyphenyl)-1,3-dioxolan-2-one (18a).
H NMR (300 MHz, CDCl ): δ 7.91 (d, J = 7.5 Hz, 2H), 7.65-7.60
m, 1H), 7.49-7.44 (m, 2H), 7.43-7.29 (m, 2H), 6.99-6.92 (m, 2H),
4
]
346.1285, found 346.1279.
3
C NMR (75 MHz, CDCl ): δ 192.0, 153.3, 134.8, 133.5, 129.2, 129.0,
7
9.9, 78.4, 34.1, 31.4, 28.7, 24.3, 22.4, 13.9. HRMS (ESI): m/z calcd for
þ
1
C H O [M þ NH ] 294.1700, found 294.1697.
16 20
4
4
3
1
4
-Benzoyl-5-octyl-1,3-dioxolan-2-one (27a). H NMR (300
MHz, CDCl ): δ 7.98 (d, J = 5.4 Hz, 2H), 7.69-7.64 (m, 1H), 7.55-
.50 (m, 2H), 5.34 (d, J = 5.4 Hz, 1H), 4.99-4.94 (m, 1H), 1.92-1.79
(
5
1
.99 (d, J = 5.1 Hz, 1H), 5.74 (d, J = 5.1 Hz, 1H), 3.96-3.89 (m, 2H),
.63-1.54 (m, 2H), 1.39-1.29 (m, 2H), 0.90 (t, J = 7.5, 7.2 Hz, 3H).
C NMR (75 MHz, CDCl ): δ 191.3, 156.3, 153.6, 134.5, 133.4, 131.1,
3
3
7
1
3
1
3
(m, 2H), 1.56-1.27 (m, 12H), 0.90-0.86 (m, 3H). C NMR (75
MHz, CDCl ): δ 192.0, 153.3, 134.7, 133.5, 129.2, 129.0, 79.9, 78.4,
129.0, 128.8, 128.0, 123.4, 120.4, 111.6, 79.6, 76.9, 67.9, 30.6, 18.9, 13.5.
3
þ
3
C
4.1, 31.7, 29.2, 29.0, 28.9, 24.4, 22.5, 14.0. HRMS (ESI): m/z calcd for
HRMS (ESI): m/z calcd for C H O [M þ NH ] 358.1649, found
20
20
5
4
þ
18
H
24
O
4
[M þ NH
4
]
322.2013, found 322.2006.
3
58.1642.
-Benzoyl-5-(2-(benzyloxy)phenyl)-1,3-dioxolan-2-one (19a).
H NMR (300 MHz, CDCl ): δ 7.80 (d, J = 7.8 Hz, 2H), 7.61-7.56 (m,
1
4
-Benzoyl-5-nonyl-1,3-dioxolan-2-one (28a). H NMR (300
4
1
MHz, CDCl ): δ 7.98 (d, J = 7.8 Hz, 2H), 7.69-7.64 (m, 1H), 7.55-7.50
3
3
(
m, 2H), 5.35 (d, J = 5.4 Hz, 1H), 4.99-4.93 (m, 1H), 1.92-1.79 (m, 2H),
1H), 7.43-7.34 (m, 4H), 7.27-7.20 (m, 5H), 7.04-6.98 (m, 2H), 6.13 (d,
13
13
1.51-1.42 (m, 2H), 1.26 (m, 12H), 0.90-0.86 (m, 3H). C NMR (75
MHz, CDCl ): δ 192.0, 153.3, 134.7, 133.5, 129.2, 129.0, 79.9, 78.4, 34.1,
1.7, 29.3, 29.2, 29.1, 28.9, 24.3, 22.6, 14.0. HRMS (ESI): m/z calcd for
J= 5.1 Hz, 1H), 5.70 (d, J= 5.1 Hz, 1H), 5.00 (dd, J= 11.7, 24.6 Hz, 2H). C
NMR (75 MHz, CDCl ): δ 191.1, 155.7, 153.6, 135.5, 134.5, 133.6, 130.9,
3
3
3
129.1, 128.8, 128.6, 128.3, 127.9, 127.6, 124.2, 121.2, 112.3, 79.7, 76.5, 70.4.
þ
4
þ
4
] 392.1492, found
C H O [M þ NH ] 336.2169, found 336.2173.
1
9
26
4
HRMS (ESI): m/z calcd for C23
H O
18 5
[M þ NH
1
4
-Benzoyl-5-undecyl-1,3-dioxolan-2-one (29a). H NMR
300 MHz, CDCl ): δ 7.99 (d, J = 8.4 Hz, 2H), 7.67 (t, J = 6.9, 7.2
Hz, 1H), 7.53 (t, J = 6.3, 7.5 Hz, 2H), 5.34 (d, J = 5.4 Hz, 1H), 4.97 (t, J =
.4, 2.7 Hz, 1H), 1.92-1.83 (m, 2H), 1.54-1.46 (m, 2H), 1.38-1.26
392.1490.
(
3
4
-Benzoyl-5-(2-isopropoxyphenyl)-1,3-dioxolan-2-one (20a).
1
H NMR (300 MHz, CDCl ): δ 7.92 (d, J = 8.4 Hz, 2H), 7.63 (t, J = 7.2
3
2
Hz, 1H), 7.49-7.45 (t, J = 7.8, 7.5 Hz, 2H), 7.37 (t, J = 7.8 Hz, 1H), 7.30
13
3
(m, 16H), 0.90-0.86 (m, 3H). C NMR (75 MHz, CDCl ): δ 192.0,
(d, J = 6.3 Hz, 1H), 6.97-6.93 (m, 2H), 5.97 (d, J = 5.7 Hz, 1H), 5.73
1
2
53.3, 134.7, 133.5, 129.2, 129.0, 79.9, 78.4, 34.1, 31.8, 29.5, 29.4, 29.3,
(d, J = 5.7 Hz, 1H), 4.63 (t, J = 6.0, 6.3 Hz, 1H), 1.30 (d, J = 6.0 Hz, 3H),
8.9, 24.4, 22.6, 14.0. HRMS (ESI): m/z calcd for C H O
13
21 30
4
1
1
7
.19 (d, J = 6.3 Hz, 3H). C NMR (75 MHz, CDCl
53.8, 134.5, 133.5, 131.0, 129.1, 128.9, 128.5, 124.3, 120.2, 112.6, 79.7,
3
): δ 191.4, 155.1,
þ
4
] 364.2482, found 364.2484.
[
M þ NH
-(Furan-2-yl)-5-benzoyl-1,3-dioxolan-2-one (30a).
NMR (300 MHz, CDCl
J = 7.5 Hz, 1H), 7.53 (d, J = 1.2 Hz, 1H), 7.45 (t, J = 7.8, 7.5 Hz, 2H), 6.63
d, J = 2.7 Hz, 1H), 6.42 (dd, J = 1.8, 2.7 Hz, 1H), 6.03 (d, J = 6.0 Hz,
1
4
H
7.2, 70.3, 21.7, 21.2. HRMS (ESI): m/z calcd for C H O [M þ
19 18 5
3
): δ 7.89 (d, J = 7.2 Hz, 2H), 7.61-7.59 (t,
þ
NH ] 344.1492, found 344.1486.
4
4
-Phenyl-5-(4-methylbenzoyl)-1,3-dioxolan-2-one (21a).
(
1
1
1
H NMR (300 MHz, CDCl ): δ 7.80 (d, J = 8.1 Hz, 2H), 7.42-7.39
13
3
3
H), 5.90 (d, J = 5.7 Hz, 1H). C NMR (75 MHz, CDCl ): δ 190.3,
(m, 5H), 7.27 (d, J = 8.4 Hz, 2H), 5.88 (d, J = 6.3 Hz, 1H), 5.60 (d, J = 6.3
52.7, 146.2, 144.8, 134.8, 132.6, 128.9, 128.8, 112.6, 110.9, 77.8, 71.9.
13
Hz, 1H), 2.41 (s, 3H). C NMR (75 MHz, CDCl
3
): δ 190.5, 153.2,
þ
HRMS (ESI): m/z calcd for C H O [M þ NH ] 276.0866, found
1
4
10
5
4
146.2, 135.5, 130.6, 129.7, 129.4, 129.3, 129.2, 125.9, 81.6, 79.0, 21.7.
2
76.0872.
4-Styryl-5-benzoyl-1,3-dioxolan-2-one (31a). H NMR
300 MHz, CDCl ): δ 7.96 (d, J = 8.4 Hz, 2H), 7.64 (t, J = 7.8 Hz,
þ
4
1
HRMS (ESI): m/z calcd for C H O [M þ NH ] 300.1230, found
17
14
4
3
00.1227.
-Phenyl-5-(4-chlorobenzoyl)-1,3-dioxolan-2-one (22a).
H NMR (300 MHz, CDCl ): δ 7.91 (d, J = 8.4 Hz, 2H), 7.49-7.41 (m,
(
3
4
1H), 7.52 (t, J = 8.4, 7.5 Hz, 2H), 7.43-7.31 (m, 5H), 6.78 (d, J = 15.6
Hz, 1H), 6.30 (dd, J = 7.5, 15.6 Hz, 1H), 5.56 (d, J = 6.0 Hz, 1H), 5.48
1
3
1
3
13
7H), 5.99 (d, J = 6.6 Hz, 1H), 5.55 (d, J = 6.3 Hz, 1H). C NMR
(t, J = 7.5 Hz, 1H). C NMR (75 MHz, CDCl ): δ 191.0, 153.1,
3
(
1
75 MHz, CDCl ): δ 190.1, 152.9, 141.6, 135.4, 131.6, 130.7, 129.9,
3
137.0, 134.8, 134.5, 133.1, 129.1, 129.0, 128.7, 127.0, 121.7, 79.8,
þ
29.4, 129.3, 125.9, 81.9, 78.8. HRMS (ESI): m/z calcd for C16
H
11ClO
4
78.9. HRMS (ESI): m/z calcd for C H O [M þ NH ] 312.1230,
1
8
14
4
4
þ
[M þ NH
4
]
-Phenyl-5-(4-bromobenzoyl)-1,3-dioxolan-2-one (23a).
320.0684, found 320.0680.
found 312.1224.
4
1
H NMR (300 MHz, CDCl ): δ 7.84 (d, J = 8.7 Hz, 2H), 7.66 (d, J = 8.7
3
’ ASSOCIATED CONTENT
Hz, 2H), 7.49-7.42 (m, 5H), 6.01 (d, J = 5.7 Hz, 1H), 5.52 (d, J = 6.0
13
S
Supporting Information. Figures and text giving char-
1 13
Hz, 1H). C NMR (75 MHz, CDCl ): δ 190.4, 152.8, 135.5, 132.5,
b
3
1
32.1, 130.8, 130.6, 129.9, 129.4, 125.9, 82.0, 78.8. HRMS (ESI): m/z
acterization data and H and C NMR spectra of new com-
pounds. This material is available free of charge via the Internet at
http://pubs.acs.org.
þ
calcd for C16
H
11BrO
4
[M þ NH
4
]
364.0179, found 364.0183.
4
-Phenyl-5-(4-methoxybenzoyl)-1,3-dioxolan-2-one (24a).
H NMR (300 MHz, CDCl ): δ 7.91 (d, J = 8.7 Hz, 2H), 7.46-7.39
m, 5H), 6.95 (d, J = 8.7 Hz, 2H), 5.94 (d, J = 6.3 Hz, 1H), 5.57 (d, J = 6.0
1
3
(
’
AUTHOR INFORMATION
13
Hz, 1H), 3.87 (s, 3H). C NMR (75 MHz, CDCl
3
): δ 189.3, 164.8, 153.2,
1
35.6, 131.7, 129.7, 129.2, 126.2, 125.9, 114.2, 81.6, 79.0, 55.6. HRMS
Corresponding Author
*E-mail: hwjing@lzu.edu.cn.
þ
4
(ESI): m/z calcd for C H O [M þ NH ] 316.1179, found 316.1178.
1
7
14
5
2
463
dx.doi.org/10.1021/jo1020294 |J. Org. Chem. 2011, 76, 2459–2464

The Journal of Organic Chemistry
ARTICLE
’
ACKNOWLEDGMENT
This research was supported by the National Natural Science
Foundation of China (NSFC 20973086).
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