The catalytic system ‘Rhodamine B/additive’ for the chemical fixation of CO2

Article abstract of DOI:10.1016/j.tet.2021.131965

The catalytic system ‘Rhodamine B/additive’ was introduced to promote the CO₂ reactions. We synthesized various cyclic carbonates in good to excellent yields under the catalysis of rhodamine B and TBAB. A variety of 2-oxazolidinone derivatives were obtained in the presence of rhodamine B and DBU.

Full text of DOI:10.1016/j.tet.2021.131965

Tetrahedron 83 (2021) 131965
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Tetrahedron
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The catalytic system ‘Rhodamine B/additive’ for the chemical fixation
of CO2
,
b
,
, **
Feng-tian Wu a, Ling Wu a *, Chun-na Cui b
a Jiangxi Province Key Laboratory of Polymer Micro/Nano Manufacturing and Devices, East China University of Technology, Nanchang, 330013, People’s
Republic of China
b Fujian Provincial Key Laboratory of Featured Biochemical and Chemical Materials, Ningde Normal University, Ningde, 352106, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
The catalytic system ‘Rhodamine B/additive’ was introduced to promote the CO2 reactions. We synthe-
sized various cyclic carbonates in good to excellent yields under the catalysis of rhodamine B and TBAB. A
variety of 2-oxazolidinone derivatives were obtained in the presence of rhodamine B and DBU.
© 2021 Elsevier Ltd. All rights reserved.
Received 6 December 2020
Received in revised form
18 January 2021
Accepted 22 January 2021
Available online 29 January 2021
Keywords:
Rhodamine B
DBU
Carbon dioxide
Cyclic carbonate
Epoxides
1. Introduction
molecular [4], quaternary ammonium salt [5], quaternary phos-
phonium salt [6], MOFs [7], hydrogen-bond donor [8,9], have been
As an abundant, nontoxic, readily available, and renewable
green C1 resource, the CO2-involved chemical transformations that
produce value-added chemicals has been paid increasing attention
[1]. Although CO2 is the thermodynamic and kinetic stability, the
following four methods can be used to activate CO2 [2]: (1) convert
CO2 into low energy products. For instance, carbonate, carbamate,
and aromatic acid. (2) push the reaction to produce the target
product by removing other products. (3) utilize high energy start-
ing material with CO2. For examples, epoxides, alkynes, and amines.
(4) other energy, such as light and heat energy, assisted the con-
version. The method to convert CO2 into low energy product such
as carbamates has been widely researched.
developed thus far. Although various catalysts have been developed
in recent years, it is still desirable to explore more efficient and
accessible catalytic systems for the chemical fixation of CO2 in mild
conditions.
Encouraged by our efforts on developing ligands to assist
copper-catalyzed CeN coupling reaction [10], and cobalt-catalyzed
the cycloaddition reaction of epoxides and CO2 [11]. We found that
Rhodamine B combined with additives could be employed as effi-
cient catalysts to catalyze CO2 reactions to synthesize cyclic car-
bonates and 2-oxazolidinone derivatives (Fig. 1).
2. Result and discussion
Catalysts present crucial function role in CO2 conversion. A va-
riety of catalytic system, such as, transition metal [3], small organic
As the reported literatures [5,8], the catalysis between
hydrogen-bond donor (abbreviated as HBD) and epoxides can
promote the step of epoxy ring-opening, which is the rate-
determining step for the cycloaddition reaction of epoxides and
CO2 (Scheme 1). Therefore, many hydrogen-bond donor com-
pounds have been developed very fast in recent years. In general,
HBD functional moieties contains eNH2, eOH, and eCOOH groups.
In hence, rhodamine B, possessing eCOOH group to activate ep-
oxides [4b], and amido group to convert CO2 into low energy
* Corresponding author. Jiangxi Province Key Laboratory of Polymer Micro/Nano
Manufacturing and Devices, East China University of Technology, Nanchang,
330013, People’s Republic of China.
** Corresponding author. Fujian Provincial Key Laboratory of Featured Biochemical
and Chemical Materials, Ningde Normal University, Ningde, 352106, People’s Re-
public of China.
E-mail address: lingwufju@163.com (L. Wu).
https://doi.org/10.1016/j.tet.2021.131965
0040-4020/© 2021 Elsevier Ltd. All rights reserved.

F.-t. Wu, L. Wu and C.-n. Cui
Tetrahedron 83 (2021) 131965
reaction under the 0.3 MPa pressure of CO2, there is no obvious
effect (entry 11). As we known that rhodamines have long been
used as photocatalysts in organic synthesis [13], the reaction was
carried out without light, the product yield was not decreased
(entry 12). Taken together, the optimal reaction conditions to
obtain 2a were under the catalysis of rhodamine B and TBAB at
100 ꢀC for 12 h.
With the optimal conditions set, we explored the substrate
scope of the cycloaddition reaction of epoxides and CO2 (Scheme 2).
By using propylethylene oxide and 1,2-hexene oxide as the re-
actants, respectively, the yields of the target compounds were ob-
tained <5%. These suggested that the length of the alkyl chains was
effective for the transformation (2b and 2c). Glycerol can partici-
pate in the reaction, but provided the desired product in moderate
yield (2d). The reactions of substrates with ester and ether sub-
stitutions smoothly provided the products (2e, 2k, 2l, 2m, and 2n).
The halogenated functional groups (F, Cl, and Br) were all
compatible under these reaction conditions (2f-2j).
Fig. 1. The structure of Rhodamine B.
The results mentioned above showed that rhodamine B can
activate CO2. Hence, we attempted to explore this catalyst to pro-
mote other reaction. As depicted in Table 2, the reaction of epox-
ides, CO2, and aromatic amine was performed at 100 ꢀC for 12 h
with the aid of rhodamine B and TBAB, but the desired product was
not obtained (entry 1). The screening of additives revealed that the
reaction was well performed with DBU as the additive (entries 1e6
vs 7). Increasing the loading of DBU to 0.5 or 1.0 mmol the product
yield was advanced to 76% and 92%, respectively (entries 8 and 9).
The yield was hardly affected when rhodamine B was reduced to 5%
mol (entry 10). Reducing the temperature to 80 ꢀC, the yield
dropped to 78% (entry 11). Notably, the yield was almost unchanged
while the CO2 pressure was 0.3 MPa (entry 12). Above all, the best
yield of 4a (90%) was provided at 100 ꢀC for 12 h by using ‘rhoda-
mine B/DBU’ as the catalytic system (entry 10).
Scheme 1. Hydrogen-bond donor aids the reaction of epoxides and CO2.
product carbamates [12], is a powerful one for the reaction of ep-
oxides and CO2 (Fig. 1).
Our study was begun by investigating 1a and CO2 at 100 ꢀC for
12 h. As shown in Table 1, only 10% yield of the desired product was
obtained without additives (entry 1). The product 2a was provided
in the absence of rhodamine B, but the yield was not good (entry 2).
The combination of rhodamine B and TBAB was better in promoting
the reaction to produce 2a in 92% yield (entry 3). Furthermore, the
four other additives were tested, and the results showed that TBAB
is the best one (entries 3 vs 4e7). After screening the reaction
temperature, the reaction was well performed at 100 ꢀC (entries 3
vs 8 and 9). When reducing the amount of Rhodamine B and TBAB
to 5% mol, the yield of 2a dropped to 67% (entry 10). Performing the
With the optimized conditions in hand, the scope of the current
conversion was explored. As shown in Scheme 3, aromatic amines
Table 1
Reaction developmenta.
Entry
Additive
Yieldb (%)
1
e
10
48
92
0
40
35
18
72
58
67
94
91
2c
3
TBAB
TBAB
TBAF
TBAC
DMAP
NEt3
TBAB
TBAB
TBAB
TBAB
TBAB
4
5
6
7
8d
9e
10f
11g
12h
a
Reaction Conditions: 1a (5.0 mmol), CO2 (balloon), rhodamine B (10% mol),
additive (10% mol), 100 ꢀC, 12 h.
b
Isolated yields.
c
Without rhodamine B.
d
e
f
80 ꢀ C
60 ꢀ C
.
.
Rhodamine B (5% mol), TBAB (5% mol).
0.3 MPa.
The reaction was performed in dark.
g
h
Scheme 2. The substrate scope of the reaction.
2

F.-t. Wu, L. Wu and C.-n. Cui
Tetrahedron 83 (2021) 131965
Table 2
Reaction optimizationa.
Entry
Additive
Yieldb (%)
1
2
3
4
5
6
7
TBAB
NEt3
DMAP
K3PO4
K2CO3
KOH
DBU
DBU
DBU
DBU
DBU
0
<5
32
34
26
18
52
76
92
90
78
93
Scheme 4. The proposed reaction mechanism.
8c
9d
10e
11f
12g
bond to form intermediate I, followed by the nucleophilic attack of
TBAB to produce intermediate II. The intermediate III from
rhodamine B and CO2 was attacked by II to generate compound IV,
which underwent intramolecular cyclization to form 2a.
DBU
a
Reaction Conditions: 1a (2.0 mmol), CO2 (balloon), 2a (2.0 mmol), rhodamineB
(10% mol), additive (10% mol),100oC,12h.
3. Conclusion
b
Isolated yields.
DBU (0.5 mmol).
DBU (1 mmol).
RhodamineB (5% mol).
80 ꢀC.
0.3 MPa.
c
d
In conclusion, the catalytic system ‘Rhodamine B/additive’-
mediated the chemical fixation of CO2 to synthesize various com-
pounds was reported. A variety of cyclic carbonates were efficiently
synthesized in good to excellent yields in the presence of rhoda-
mine B and TBAB. A wide range of 2-oxazolidinone derivatives were
obtained with the aid of rhodamine B and DBU.
e
f
g
4. Experimental section
4.1. General remarks
Unless otherwise stated, all reagents were purchased from
commercial suppliers and used without further purification. Col-
umn chromatography was performed with silica gel (200e300
mesh) purchased from Qingdao Haiyang Chemical Co. Ltd. Thin-
layer chromatography was carried out with Merck silica gel GF254
plates. 1H and 13C spectra were recorded on a Bruker AV-400. Mass
spectra were recorded on GC-MS (Agilent 7890 A/5975C) instru-
ment under EI model.
4.2. The general procedure for the coupling reaction of styrene
oxide and CO2
In a typical reaction, CO2 (balloon) and styrene oxide (5 mmol)
was mixed with rhodamine B (0.5 mmol), TBAB (0.5 mmol) in a
25 mL in a glass tubular reactor equipped with a magnetic stir bar.
And then, the mixture was stirred at 100 ꢀC for 12 h. After the re-
action, the mixture was diluted with H2O (10 mL), and extracted
with ethyl acetate (3 ꢁ 20 mL). The combined organic phases were
washed with water and brine, dried over anhydrous Na2SO4, and
concentrated in vacuo. The residue was purified by flash column
chromatograph on silica gel to afford the target product 2a. Syn-
thesis of other compounds 2b-2o was performed by an analogous
procedure.
Scheme 3. Three-component reaction of 1, CO2, and 3.
possessing fluoro, chloro, bromo, or iodo groups produced the
desired compounds under the optimal conditions, respectively (4b-
4e). Substrates with electron-donating groups presented better
reactivity than those with electron-withdrawing ones (4b-4c vs 4f-
4h). Slightly low yield was observed with sterically demanding
substrate (4f vs 4g), but the reaction did not occur when o-toluidine
was as the reactant. When ammonia water and propylene oxide
were utilized as the reactants, the corresponding compounds were
separately given (4i and 4j).
4.3. The general procedure for the reaction of styrene oxide, CO2,
and aniline
In a typical reaction, CO2 (balloon), aniline (5 mmol), and sty-
rene oxide (5 mmol) was mixed with rhodamine B (0.1 mmol), DBU
(1 mmol) in a 25 mL in a glass tubular reactor equipped with a
magnetic stir bar. And then, the mixture was stirred at 100 ꢀC for
12 h. After the reaction, the mixture was diluted with H2O (10 mL),
On the basis of previous reported literatures [8,12], the plausible
reaction mechanism between 1a and CO2 was proposed in Scheme
4. Initially, rhodamine B activated 1a by the function of hydrogen
3

F.-t. Wu, L. Wu and C.-n. Cui
Tetrahedron 83 (2021) 131965
and extracted with ethyl acetate (3 ꢁ 20 mL). The combined organic
phases were washed with water and brine, dried over anhydrous
Na2SO4, and concentrated in vacuo. The residue was purified by
flash column chromatograph on silica gel to afford the target
product 4a. Synthesis of other compounds 4b-4j was performed by
an analogous procedure.
4.4.9. 4-(4-Chlorophenyl)-1,3-dioxolan-2-one [14] (2i)
Light yellow oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
¼ 7.56e7.58 (m, 2H), 7.34e7.36 (m 2H), 5.77 (t, J ¼ 8.0 Hz,1H), 4.82
d
(t, J ¼ 8.0 Hz, 1H), 4.32 ppm (t, J ¼ 8.0 Hz, 1H); 13C NMR (100 MHz,
DMSO‑d6, 25 ꢀC):
d
¼ 155.1, 136.2, 132.3, 129.4, 123.1, 77.5, 71.1 ppm;
GC-MS (EI): m/z ¼ 198 [M]þ.
4.4. The 1H NMR, 13C NMR, and EI-MS spectra data of products
4.4.10. 4-(4-Bromophenyl)-1,3-dioxolan-2-one [14] (2j)
Light colorless oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.74e7.76 (m, 2H), 7.54e7.56 (m 2H), 5.96 (t, J ¼ 8.0 Hz, 1H),
4.4.1. 4-Phenyl-1,3-dioxolan-2-one [14] (2a)
4.96e5.00 (m, 1H), 4.47e4.51 ppm (m, 1H); 13C NMR (100 MHz,
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.49e7.51
DMSO‑d6, 25 ꢀC):
d
¼ 155.4, 136.1, 134.8, 132.6, 129.7, 129.4, 77.8,
(m, 2H), 7.41e7.48 (m, 3H), 5.87 (t, J ¼ 6.4 Hz, 1H), 4.90 (t, J ¼ 6.8 Hz,
77.5 ppm; GC-MS (EI): m/z ¼ 241 [M]þ.
1H), 4.42 ppm (t, J ¼ 6.8 Hz; 1H); 13C NMR (100 MHz, DMSO‑d6,
25 ꢀC):
d
¼ 154.9, 136.4, 129.5, 129.0, 126.7, 77.9, 71.0 ppm; GC-MS
(EI): m/z ¼ 174 [M]þ.
4.4.11. 4-(Phenoxymethyl)-1,3-dioxolan-2-one [14] (2k)
Light colorless oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.28e7.32 (m, 2H), 6.94e6.98 (m 3H), 5.11e5.17 (m, 1H), 4.62 (t,
4.4.2. 4-Methyl-1,3-dioxolan-2-one [14] (2b)
J ¼ 8.0 Hz, 1H), 4.25e4.29 (m, 1H), 4.17e4.21 ppm (m, 1H); 13C NMR
Colorless oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
(100 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 162.7, 159.6, 134.3, 126.0, 119.4,
d
¼ 4.86e4.94 (m, 1H), 4.57 (t, J ¼ 8.0 Hz,1H), 4.06 (t, J ¼ 8.0 Hz, 1H),
79.6, 72.2, 70.7 ppm; GC-MS (EI): m/z ¼ 194 [M]þ.
1.37 ppm (d, J ¼ 6.4 Hz, 3H); 13C NMR (100 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 155.4, 74.2, 70.9, 19.2 ppm; GC-MS (EI): m/z ¼ 102 [M]þ.
4.4.12. 4-((Benzyloxy)methyl)-1,3-dioxolan-2-one [17] (2l)
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.25e7.36
(m, 5H), 4.89e4.94 (m, 1H), 4.53 (s, 2H), 4.48e4.52 (m, 1H),
4.26e4.29 (m, 1H), 3.66e3.70 (m, 1H), 3.57e3.61 ppm (m, 1H); 13
4.4.3. 4-Ethyl-1,3-dioxolan-2-one [14] (2c)
Colorless oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 4.70e4.77
C
NMR (100 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 155.4, 138.2, 128.7, 128.0,
(m, 1H), 4.56 (t, J ¼ 8.0 Hz, 1H), 4.14 (t, J ¼ 8.0 Hz, 1H), 1.67e1.75 (m,
J ¼ 6.8 Hz, 2H), 0.92 ppm (t, J ¼ 7.2 Hz; 3H); 13C NMR (100 MHz,
127.8, 75.9, 72.9, 69.6, 66.5 ppm; GC-MS (EI): m/z ¼ 208 [M]þ.
DMSO‑d6, 25 ꢀC):
m/z ¼ 116 [M]þ.
d
¼ 155.4, 78.4, 69.2, 26.4, 8.6 ppm; GC-MS (EI):
4.4.13. 4-((Allyloxy)methyl)-1,3-dioxolan-2-one [15] (2m)
Brown oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 5.82e5.92
4.4.4. 4-(Hydroxymethyl)-1,3-dioxolan-2-one [14] (2d)
Colorless oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
(m, 1H), 5.23e5.27 (m, 1H), 5.16 (d, J ¼ 8.0 Hz, 2H), 4.90e4.95 (m,
1H), 4.52 (t, J ¼ 8.0 Hz, 1H), 4.00 (d, J ¼ 6.4 Hz, 2H), 3.63e3.66 (m,
1H), 3.55e3.58 ppm (m, 1H); 13C NMR (100 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 5.21e5.24
(m, 1H), 4.75e4.79 (m, 1H), 4.45e4.49 (m, 1H), 4.26e4.29 (m, 1H),
3.63e3.68 (m, 1H), 3.47e3.52 ppm (m, 1H); 13C NMR (100 MHz,
d
¼ 155.4, 135.1, 117.2, 75.9, 71.8, 69.6, 66.5 ppm; GC-MS (EI): m/
DMSO‑d6, 25 ꢀC):
z ¼ 118 [M]þ.
d
¼ 155.6, 77.5, 66.3, 61.0 ppm; GC-MS (EI): m/
z ¼ 158 [M]þ.
4.4.14. (2-Oxo-1,3-dioxolan-4-yl)methyl methacrylate [18] (2n)
Light brown oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 6.03 (s,
4.4.5. 4-(Methoxymethyl)-1,3-dioxolan-2-one [15] (2e)
Colorless oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
1H), 5.72 (s, 1H), 5.07e5.12 (m, 1H), 4.58 (t, J ¼ 8.4 Hz, 1H),
4.28e4.40 (m, 3H),1.87 ppm (m, 3H); 13C NMR (100 MHz, DMSO‑d6,
d
¼ 4.88e4.93 (m, 1H), 4.51 (t, J ¼ 8.0 Hz, 1H), 4.23e4.26 (m, 1H),
25 ꢀC):
d
¼ 166.5, 155.2, 135.8, 126.9, 74.6, 66.6, 64.4, 18.2 ppm; GC-
3.57e3.61 (m, 1H), 3.48e3.53 (m, 1H), 3.31 ppm (s, 3H); 13C NMR
MS (EI): m/z ¼ 186 [M]þ.
(100 MHz, DMSO‑d6, 25 ꢀC):
GC-MS (EI): m/z ¼ 132 [M]þ.
d
¼ 155.4, 75.8, 71.8, 66.4, 59.1 ppm;
4.4.15. Hexahydrobenzo[d][1,3]dioxol-2-one [15] (2o)
1
Colorless oil; H NMR (400 MHz, CDCl3, 25 ꢀC):
d
¼ 4.55e4.60
4.4.6. 4-(Chloromethyl)-1,3-dioxolan-2-one [14] (2f)
(m, 2H), 1.76e1.78 (m, 3H), 1.46e1.54 (m, 2H), 1.29e1.34 (m, 2H),
1
Colorless oil; H NMR (400 MHz, CDCl3, 25 ꢀC):
d
¼ 4.85e4.91
1.13e1.25 ppm (m,1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
75.8, 26.7, 19.1 ppm; GC-MS (EI): m/z ¼ 142 [M]þ.
d
¼ 155.4,
(m, 1H), 4.48 (t, J ¼ 8.0 Hz, 1H), 4.27e4.31 (m, 1H), 3.59e3.72 ppm
(m, 2H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼ 155.4, 75.8, 71.8,
66.4, 59.1 ppm; GC-MS (EI): m/z ¼ 136 [M]þ.
4.4.16. 3,5-Diphenyloxazolidin-2-one [19] (4a)
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.59e7.61
4.4.7. 4-(Bromomethyl)-1,3-dioxolan-2-one [16] (2g)
(m, 2H), 7.38e7.53 (m, 7H), 7.12e7.16 (m,1H), 5.76 (t, J ¼ 8.0 Hz,1H),
Colorless oil; 1H NMR (400 MHz, CDCl3, 25 ꢀC):
d
¼ 4.91e4.96
4.48 (t, J ¼ 8.4 Hz, 1H), 4.01 ppm (t, J ¼ 8.0 Hz, 1H); 13C NMR
(100 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 154.2, 138.3, 128.8, 128.7, 126.4,
(m, 1H), 4.53 (t, J ¼ 8.0 Hz, 1H), 4.24e4.28 (m, 1H), 3.58e3.62 (m,
1H), 3.50e3.54 ppm (m, 1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
123.6, 118.2, 73.8, 51.7 ppm; GC-MS (EI): m/z ¼ 239 [M]þ.
d
¼ 154.6, 74.2, 68.2, 32.4 ppm; GC-MS (EI): m/z ¼ 179 [M]þ.
4.4.17. 3-(4-Fluorophenyl)-5-phenyloxazolidin-2-one [20] (4b)
4.4.8. 4-(4-Fluorophenyl)-1,3-dioxolan-2-one [16] (2h)
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.60e7.63
d
¼ 7.65e7.68
(m, 2H), 7.49e7.51 (m, 2H), 7.37e7.46 (m, 3H), 7.21e7.25 (m, 2H),
(m, 2H), 7.39 (t, J ¼ 8.8 Hz, 2H), 5.97 (t, J ¼ 8.0 Hz, 1H), 4.96 (t,
5.74 (t, J ¼ 8.0 Hz,1H), 4.44 (t, J ¼ 8.4 Hz,1H), 3.99 ppm (t, J ¼ 8.4 Hz,
13
J ¼ 8.0 Hz, 1H), 4.52 ppm (t, J ¼ 8.0 Hz, 1H); 13C NMR (100 MHz,
1H); C NMR (100 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 160.1, 157.7, 154.8,
DMSO‑d6, 25 ꢀC):
d
¼ 163.8, 161.3, 154.6, 132.4, 129.2 (JC-F ¼ 10.1 Hz),
138.7, 135.3, 129.3 (JC-F ¼ 12.6 Hz), 126.9, 120.7 (JC-F ¼ 10.1 Hz), 116.1,
115.7 (JC-F ¼ 27.7 Hz), 77.2, 70.7 ppm; 19F NMR (376 MHz, DMSO‑d6,
115.9, 74.3, 52.4 ppm; 19F NMR (376 MHz, DMSO‑d6, 25 ꢀC):
25 ꢀC):
d
¼ ꢂ114.1 ppm; GC-MS (EI): m/z ¼ 182 [M]þ.
d
¼ ꢂ129.9 ppm; GC-MS (EI): m/z ¼ 257 [M]þ.
4

F.-t. Wu, L. Wu and C.-n. Cui
Tetrahedron 83 (2021) 131965
4.4.18. 3-(4-Chlorophenyl)-5-phenyloxazolidin-2-one [20] (4c)
Light yellow solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
Acknowledgments
d
¼ 7.64e7.66 (m, 2H), 7.52e7.53 (m, 2H), 7.40e7.48 (m, 5H), 5.77 (t,
J ¼ 8.0 Hz, 1H), 4.47 (t, J ¼ 8.4 Hz, 1H), 4.01 ppm (t, J ¼ 8.0 Hz, 1H);
13C NMR (100 MHz, DMSO‑d6, 25 ꢀC):
This work was sponsored by the Jiangxi Provincial Natural Sci-
ence Foundation (20202BABL213021) and the Opening Fund Proj-
ect of Fujian Provincial Key Laboratory of Featured Biochemical and
d
¼ 154.6, 148.1, 138.6, 137.8,
129.4, 129.3, 129.2, 129.0, 128.0, 126.9, 120.2, 115.6, 115.9, 74.4,
Chemical
Materials,
Ningde
Normal
University
(FJKL-
52.1 ppm; GC-MS (EI): m/z ¼ 273 [M]þ.
FBCM202008).
4.4.19. 3-(4-Bromephenyl)-5-phenyloxazolidin-2-one [20] (4d)
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.58e7.59
Appendix A. Supplementary data
(m, 4H), 7.42e7.54 (m, 5H), 5.77 (t, J ¼ 8.0 Hz,1H), 4.47 (t, J ¼ 8.4 Hz,
1H), 4.01 ppm (t, J ¼ 8.0 Hz, 1H); 13C NMR (100 MHz, DMSO‑d6,
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2021.131965.
25 ꢀC):
d
¼ 154.6, 138.6, 138.2, 132.1, 129.4, 129.3, 126.9, 120.6, 116.0,
þ
74.4, 52.1 ppm; GC-MS (EI): m/z ¼ 317 [M]
.
4.4.20. 3-(4-Iodophenyl)-5-phenyloxazolidin-2-one [20] (4e)
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
References
d
¼ 7.62e7.64
(m, 2H), 7.41e7.52 (m, 7H), 5.76 (t, J ¼ 8.0 Hz, 1H), 4.46 (t, J ¼ 8.4 Hz,
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(2014) 2330e2333;
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157e168.
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4211e4220;
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1895e1906;
1H), 4.00 ppm (t, J ¼ 8.0 Hz, 1H); 13C NMR (100 MHz, DMSO‑d6,
25 ꢀC):
d
¼ 154.1, 138.1, 137.3, 128.9, 128.8, 128.7, 127.5, 126.4, 119.7,
73.9, 51.6 ppm; GC-MS (EI): m/z ¼ 364 [M]þ.
4.4.21. 5-Phenyl-3-(p-tolyl)oxazolidin-2-one [20] (4f)
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.37e7.49
(m, 7H), 7.17e7.19 (m, 2H), 5.72 (t, J ¼ 8.0 Hz, 1H), 4.42 (t, J ¼ 8.4 Hz,
1H), 3.94 (t, J ¼ 8.0 Hz, 1H), 2.26 ppm (s, 3H); 13C NMR (100 MHz,
DMSO‑d6, 25 ꢀC):
d
¼ 154.2, 138.4, 135.9, 132.7, 129.3, 128.8, 128.7,
126.3, 118.2, 73.7, 51.8, 20.3 ppm; GC-MS (EI): m/z ¼ 253 [M]þ.
b) N. Liu, Y.-F. Xie, C. Wang, S.-J. Li, D. Wei, M. Li, B. Dai, ACS Catal. 8 (2018)
9945e9957.
[5] a) F. Liu, Y. Gu, P. Zhao, J. Gao, M. Liu, ACS Sustain. Chem. Eng. 7 (2019)
5940e5945;
b) J. Hua, J. Ma, H. Liu, Q. Qian, C. Xie, B. Han, Green Chem. 20 (2018)
2990e2994.
[6] a) W. Dai, W. Yang, Y. Zhang, D. Wang, X. Luo, X. Tu, J. CO2 Util. 17 (2017)
256e262;
4.4.22. 5-Phenyl-3-(m-tolyl)oxazolidin-2-one [20] (4g)
Colorless oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.37e7.50
(m, 7H), 7.24e7.28 (m, 1H), 6.93e6.95 (m, 1H), 5.73 (t, J ¼ 8.0 Hz,
1H), 4.43 (t, J ¼ 8.4 Hz, 1H), 3.96 (t, J ¼ 8.0 Hz, 1H), 2.30 ppm (s, 3H);
13C NMR (100 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 154.7, 138.9, 138.8, 138.7,
b) Z. Zhang, F. Fan, H. Xing, Q. Yang, Z. Bao, Q. Ren, ACS Sustain. Chem. Eng. 5
(2017) 2841e2846.
129.3, 129.2, 129.1, 126.8, 124.8, 119.2, 115.9, 74.2, 52.3, 21.7 ppm;
GC-MS (EI): m/z ¼ 253 [M]þ.
[7] a) G. Zhang, H. Yang, H. Fei, ACS Catal. 8 (2018) 2519e2525;
b) S. Bhunia, R.A. Molla, V. Kumari, S.M. Islamb, A. Bhaumik, Chem. Commun.
51 (2015) 15732e15735.
ꢀ
4.4.23. 3-(4-Methoxyphenyl)-5-phenyloxazolidin-2-one [20] (4h)
[8] a) A. Mesías-Salazar, J. Martínez, R.S. Rojas, F. Carrillo-Hermosilla, A. Ramos,
White solid; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.40e7.52
ꢀ
ꢀ
~
R. Fernandez-Galan, A. Antinolo, Catal. Sci. Technol. 9 (2019) 3879e3886;
(b) N. Fanjul-Mosteirín, C. Jehanno, F. Ruiperez, H. Sardon, A.P. Dove, ACS
Sustain. Chem. Eng. 7 (2019) 10633e10640;
(m, 7H), 6.96e6.99 (m, 2H), 5.74 (t, J ¼ 8.0 Hz,1H), 4.43 (t, J ¼ 8.4 Hz,
1H), 3.96 (t, J ¼ 8.0 Hz, 1H), 3.75 ppm (s, 3H); 13C NMR (100 MHz,
c) Y. Fan, M. Tiffner, J. Schorgenhumer, R. Robiette, M. Waser, S.R. Kass, J. Org.
Chem. 83 (2018) 9991e10000.
DMSO‑d6, 25 ꢀC):
d
¼ 156.2, 154.9, 138.9, 131.9, 129.3, 126.8, 120.7,
114.5, 74.2, 55.7, 52.6 ppm; GC-MS (EI): m/z ¼ 269 [M]þ.
[9] a) M. Alvesa, B. Grignard, S. Gennenb, R. Mereaua, C. Detrembleur, C. Jerome,
T. Tassaing, Catal. Sci. Technol. 5 (2015) 4636e4643;
b) H. Sun, D.J. Zhang, J. Phys. Chem. 111 (2007) 8036e8043.
[10] a) F. Wu, C. Nan, M. Ma, H. Li, J. Xie, Appl. Oranomet. Chem. 33 (2019) e5195;
b) F. Wu, J. Xie, Z. Zhu, Appl. Oranomet. Chem. 34 (2020), e5926;
c) F. Wu, Appl. Oranomet. Chem. 34 (2020) e5975;
d) F. Wu, M. Ma, J. Xie, Asian J. Org. Chem. 8 (2019) 755e766;
e) J. Xie, X. Wang, F. Wu, J. Zhang, Chin. J. Org. Chem. 39 (2019) 3026e3039.
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[12] L. Ji, Z. Luo, Y. Zhang, R. Wang, Y. Ji, F. Xia, G. Gao, Mol. Catal. 446 (2018)
124e130.
4.4.24. 3-(4-Methoxyphenyl)-5-phenyloxazolidin-2-one [21] (4i)
1
Colorless oil; H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
d
¼ 7.69 (s,
1H), 7.34e7.43 (m, 5H), 5.28 (t, J ¼ 8.4 Hz, 1H), 3.87 (t, J ¼ 8.4 Hz,
1H), 3.32 ppm (t, J ¼ 8.0 Hz, 1H); 13C NMR (100 MHz, DMSO‑d6,
25 ꢀC):
d
¼ 159.2, 139.8, 129.2, 128.9, 126.3, 76.8, 47.9 ppm; GC-MS
(EI): m/z ¼ 163 [M]þ.
[13] H. Shigemitsu, Y. Tani, T. Tamemoto, T. Mori, X. Li, Y. Osakada, M. Fujitsuk,
T. Kida, Chem. Sci. 11 (2020) 11843e11848.
4.4.25. 5-Methyl-3-phenyloxazolidin-2-one [22] (4j)
ꢀ
ꢀ
[14] M.A. Gaona, F. de la Cruz-Martínez, J. Fernandez-Baeza, L.F. Sanchez-Barba,
Light brown oil; 1H NMR (400 MHz, DMSO‑d6, 25 ꢀC):
ꢀ
C. Alonso-Moreno, A.M. Rodríguez, A. Rodríguez-Dieguez, J.A. Castro-Osma,
A. Otero, A. Lara-Sanchez, Dalton Trans. 48 (2019) 4218e4227.
[15] R. Gerardy, J. Estager, P. Luis, D.P. Debecker, J.-C.M. Monbaliu, Catal. Sci.
d
¼ 7.54e7.56 (m, 2H), 7.36e7.40 (m, 2H), 7.09e7.13 (m, 1H),
ꢀ
ꢀ
4.75e4.83 (m, 1H), 4.15 (t, J ¼ 8.4 Hz, 1H), 3.66 (t, J ¼ 8.4 Hz, 1H),
Technol. 9 (2019) 6841e6851.
1.41 ppm (d, J ¼ 2.4 Hz, 3H); 13C NMR (100 MHz, DMSO‑d6, 25 ꢀC):
[16] L. Martnez-Rodrguez, J.O. Garmilla, A.W. Kleij, ChemSusChem
9 (2016)
d
¼ 154.9, 139.1, 129.3, 123.8, 118.4, 70.1, 51.5, 20.6 ppm; GC-MS (EI):
749e755.
m/z ¼ 177 [M]þ.
[17] H. Ullah, B. Mousavi, H.A. Younus, Z.A.K. Khattak, S. Suleman, M.T. Jan, B. Yu,
S. Chaemchuen, F. Verpoort, J. Catal. 377 (2019) 190e198.
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Commun. (2007) 2175e2177.
Declaration of competing interest
[19] A.W. Miller, S.T. Nguyen, Org. Lett. 6 (2004) 2301e2304.
[20] F. Li, X. Li, C. Xu, S.M. Sadeghzadeh, Catal. Lett. 150 (2020) 1729e1740.
[21] R.A. Watile, D.B. Bagal, Y.P. Patil, B.M. Bhanage, Tetrahedron Lett. 52 (2011)
6383e6387.
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
[22] Y. Song, C. Cheng, H. Jing, Chem. Eur J. 20 (2014) 12894e12900.
5