Bifunctional organocatalysts for the conversion of CO2, epoxides and aryl amines to 3-aryl-2-oxazolidinones

Article abstract of DOI:10.1039/c9ob00224c

A route to synthesize 3-aryl-2-oxazolidinones is developed, which is achieved through a three component reaction between CO₂, aryl amines, and epoxides with a binary organocatalytic system composed of organocatalysts and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The method allows wide scopes of epoxide and aryl amine substrates with various functional groups under mild reaction conditions. The control experiments indicate that a cyclic carbonate is formed via cycloaddition of epoxides with CO₂, which further reacts with the β-amino alcohol originating from epoxides and aryl amines, resulting in the formation of 3-aryl-2-oxazolidinones finally.

Full text of DOI:10.1039/c9ob00224c

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Bifunctional organocatalysts for conversion of CO2, epoxides and
aryl amines to 3-aryl-2-oxazolidinones
Ya-Fei Xie,a Cheng Guo,b Lei Shi,a Bang-Hua Peng,*a and Ning Liu*a
Received 00th January 20xx,
Accepted 00th January 20xx
A route to synthesize 3-aryl-2-oxazolidinones is developed, which is achieved through three component reaction between
CO2, aryl amines, and epoxides with a binary organocatalytic system composed of organocatalyts and DBU (1,8-
diazabicyclo[5.4.0]undec-7-ene). The method allows wide scopes of epoxide and aryl amine substrates with various
functional group in the mild reaction conditions. The control experiments indicate that a cyclic carbonate is formed via
cycloaddition of epoxides with CO2, which further reacts with the -amino alcohol originated from epoxides and aryl amines,
resulting in the formation of 3-aryl-2-oxazolidinones finally.
DOI: 10.1039/x0xx00000x
www.rsc.org/
We have reported
a new family of multifunctional
Introduction
organocatalysts that allows the cycloaddition between CO2 and
epoxides under ambient conditions.18 Inspired by our previously
reported work, we became interested in the catalytic activity in
the three component reaction between CO2, aryl amines, and
epoxides. Here, we demonstrate that the organocatalysts were
highly active for the three component reaction between CO2,
aryl amines, and epoxides under mild reaction condition (90°C),
together with broad substrates scope.
The oxazolidinone heterocycles are important organic
molecules in pharmaceutically active compounds and are
widely used as Linezolid (antibacterial agents), and Toloxatone
(antidepressant).1
The use of carbon dioxide as starting materials has emerged as
an environmentally friendly method for synthesis of value-
added chemicals.2 The unique biological activities in the
medicines containing oxazolidinone heterocycles has
encouraged the development and application of many synthetic
strategies (Figure 1),3 such as using N-aziridines,4
propargylamines,5 allyl amines,6 allenamines,7 propargylic
O
R
N
ArNH2
+
R
O
NHR
alcohols,8
dibromoalkanes,9
epoxy
amines,10
and
ref. 3
O
ref. 9
ref. 8
multicomponent cycloaddition of alkyne.11 Among the existing
methods, the use of the three component reaction between
CO2, aryl amines, and epoxides has emerged as an alternative
tool that affords access to the oxazolidinone heterocycles.
Since the first example of the direct conversion of CO2, anilines,
and epoxides to the 3-aryl-2-oxazolidinones with the binary
ionic liquids catalytic systems,12 various catalysts, such as DBU
R1
(R)H
N
O
NHR
ArNH2
ref. 4
R3
R2
+
X
X
R
R
R
ref.
5
CO2
X = Br, Cl
(R)H
NH
R
ref. 6
ref. 7
R
NH
(1,8-diazabicyclo[5.4.0]undec-7-ene)/DBU-derived
bromide
ionic liquid,13 K3PO4,14 DBU/TBAI (tetrabutylammonium
iodide),15 Arthrospira-supported ionic liquid,16 and Fe(II)
complexes/DBU,17 have been developed for the synthesis of the
3-aryl-2-oxazolidinones.
OH
Figure 1 Synthetic method for the oxazolidinone heterocycles.
Results and discussion
Organocatalysts 1a-g with different electronic properties were
prepared as reported previously.18 Organocatalysts 1a-g were
first tested as catalysts for the cycloaddition reaction of CO2,
anilines, and propylene oxide (PO) 2a at 90 °C and 5 bar a CO2
pressure (Table 1, entries 1-7). The combination of
organocatalyst 1e and DBU as cocatalyst was found to be the
most efficient catalyst system. Control experiments indicated
that neither organocatalyst 1e nor DBU showed highly catalytic
activity in the absence of the other catalyst component (Table
a. School of Chemistry and Chemical Engineering, Key Laboratory for Green
Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi University, North
Fourth Road, Shihezi, Xinjiang 832003, People’s Republic of China. Corresponding
Authors: Ning Liu: ningliu@shzu.edu.cn; ninglau@163.com; Bang-Hua Peng:
banghuapeng@163.com.
b. Address Cancer Institute, The Second Affiliated Hospital, Zhejiang University
School of Medicine, Hangzhou, Zhejiang 310009, People’s Republic of China.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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1, entries 8 and 9). A decrease in the product yield was observed When the CO2 pressure was reduced from 5 baVrietwoAr3ticlbe aOrn,linae
DOI: 10.1039/C9OB00224C
by lowering the reaction temperature from 90 °C to 80 °C; even slightly lower yield was observed (Table 1, entries 5 and 13). So
if the reaction time is prolonged, it is difficult to achieve we carried out the model reaction under atmospheric pressure
excellent results under 90 °C (Table 1, entries 5 vs 10 and 11). of CO2, but only 36% yield of product (Table 1, entry 14). We
The ratio of the catalyst 1e to the substrates significantly found that the low boiling point of propylene oxide is
influenced the reaction rate. A declination in the catalytic responsible for the poor result. So higher boiling point of
activity was observed by decreasing the amount of catalyst 1e butylene oxide is investigated under atmospheric pressure of
from 2.5 mol% to 1.25 mol% (Table 1, entries 5 vs 12).
CO2, and a 75% yield of product was obtained (Table 1, entry 15).
To our delight, the catalyst loading has an obviously promoted
effect on reaction rate. When the catalyst loading of 1e was
increased from 2.5 to 5 mol % and cocatalyat of DBU from 20 to
30 mol%, the yield of 4m reached 95% under atmospheric
pressure of CO2 (Table 1, entry 16).
Table 1 Optimization of reaction conditionsa
O
H2N
O
CO2
2
Ph
N
OH
O
+
+
R
OH
R
R
2a
3a
4a
The search for catalytic systems for the direct conversion of CO2,
anilines, and epoxides to the 3-aryl-2-oxazolidinones started
with the discovery of Gao and co-workers in 2014 using the
binary ionic liquids of 1-butyl-3-methyl-imidazolium bromide
and 1-butyl-3-methyl-imidazolium acetate (Table 2, entry 1).12
However, this catalytic system and this reported in 201613
operate under relatively harsh reaction conditions (> 140 °C, 25
bar CO2), and a poor substrate of epoxides scope is reported
(Table 2, entries 1 and 2). Recently, the search for efficient
catalytic systems operating under milder reaction conditions, in
particular low pressure of CO2, has stimulated much interest,
and significant progress has been achieved. Two important
contributions have been significantly improved to atmospheric
pressure of CO2 using simple inorganic base of K3PO4 described
by Chung co-workers14 at 130°C under atmospheric pressure of
CO2 (Table 2, entry 3) and the binary system using TBAI in
combination with one equivalent of DBU reported by Yao and
co-workers at 115 °C under atmospheric pressure of CO2 (Table
2, entry 4).15 However, there are still issues to overcome: (i)
K3PO4 catalytic system is difficult to control the regioselectivity
in reaction, (ii) One equivalent of DBU is often needed in
TBAI/DBU catalytic system. In this work, we have developed a
binary organocatalytic system 1e combined with DBU, which
has shown to efficiently promote the direct conversion of CO2,
anilines, and epoxides to the 3-aryl-2-oxazolidinones at 90°C
under atmospheric pressure of CO2, together with good
functional-group tolerance and broad substrate scope (Table 2,
entry 5).
, R1 = Me, R2 = Me, X = I
1a
1b
1c
1d
1e
1f
, R1 = H, R2 = i-Pr, X = I
HO
O
, R1 = H, R2 = CH2SCH3, X = I
, R1 = H, R2 = Ph, X = I
R1
N
I
N
N
H
R2
N
, R1 = H, R2 = 4-OH-Ph, X = I
, R1 = H, R2 = 4-OH-Ph, X = Br
, R1 = H, R2 = 4-OH-Ph, X = Cl
1g
T
(h
)
Entr
y
Cat.
(mmol)
Cocat
.
T
P
Yield
(%)
R
(°C) (bar)
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
1a (0.05)
1b (0.05)
1c (0.05)
1d (0.05)
1e (0.05)
1f (0.05)
1g (0.05)
1e (0.05)
DBU
DBU
DBU
DBU
DBU
DBU
DBU
90
90
90
90
90
90
90
90
90
80
80
90
90
90
90
90
5
5
5
5
5
5
5
5
5
5
5
5
3
1
1
1
4
4
4
4
4
4
4
4
4
4
8
4
4
63
52
72
86
95
59
36
0
1
2
3
4
5
6
7
8
DBU
DBU
DBU
5
9
1e (0.05)
1e (0.05)
80
83
43
87
10
11
12
13
14b
15b
16c
1e (0.025) DBU
1e (0.05)
1e (0.05)
1e (0.05)
1e (0.1)
DBU
DBU
DBU
DBU
25 36
25 75
25 95
Et
aReaction condition: aniline (2 mmol), propylene oxide (2 mL),
catalyst (as indicated in this table), DBU (0.4 mmol), CO2 (the
reaction carried out in a 25 mL stainless steel autoclave). CO2
balloon. cCO2 balloon, 1e (0.1 mmol), DBU (0.6 mmol).
b
Table 2 Comparison of the efficiency, and scope between previously reported catalytic systems and bifunctional organocatalysts
in this work
entry author
1
Catalyst/amine
BmimBr (10 mol%)
Cocatalyst/amine
BminOAc (10 mol%) 140
130
HDBUBr (5 mol%)
160
none
T (°C)
P (bar)
Substrate scope
ethylene oxide
ethylene oxide
propylene oxide
excellent
Regioselectivity
excellent
Gao12
25
25
25
1
2
Gao13
DBU (20 mol%)
excellent
3
4
Chung14 K3PO4 (20 mol%)
130
115
poor
excellent
Yao15
This
TBAI (5 mol%)
DBU (100 mol%)
1
excellent
5
1e (5 mol%)
DBU (30 mol%)
90
1
excellent
excellent
work
2 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C9OB00224C
Table 3 Scope of substrates
R2
O
NH2
OH
O
2
R2
CO2
2
O
N
+
+
OH
R1
R1
R1
3
4
O
O
O
F
O
O
OMe
Me
OEt
O
N
O
N
O
N
O
N
O
N
Me
Me
Me
Me
Me
4e, >99%
4d, 93%
4a, 95%
4c, 87%
4b,85%
O
O
N
O
O
I
Br
Cl
O
O
O
N
O
N
O
N
O
N
Me
NO2
Me
Me
Me
Me
Me
4i, 75%
4j, 91%
4f, >99%
4h, >99%
4g, >99%
O
Cl
O
N
O
O
N
O
O
O
N
O
O
N
O
N
Cl
O
nBu
4n, 81% (96%b)
Et
Me
Me
nBu
4o, 87% (93%b)
4m, 80% (95%b)
4l, 89%
O
4k, >99%
O
O
O
O
N
O
N
O
N
O
N
O
Cl
F
4s, 43% (91%b)
4p, 85% (89%b)
4q, 37% (88%b)
4r, 47% (95%b)
O
O
O
N
O
O
O
N
O
N
O
N
N
Me
Me
Br
4w, trace
4v, trace
4t, 45% (96%b)
4u, 75%
a Reaction condition: aryl amine (2 mmol), terminal epoxides (2 mL), 1e (0.05 mmol), DBU (0.4 mmol), 90 °C, CO2 (5 bar), 4 h. bCO2
balloon, 1e (0.1 mmol), DBU (0.6 mmol).
Under 90 °C and 5 bar of CO2, we selected PO as the model obtained in good to excellent yields. The meta-substituted aryl
substrate for investigation of the scope of aryl amines as shown amines bearing electron-donating groups (Table 3, entry 4i)
in Table 3. First, various aryl amines 3 were examined to explore presented lower reactivity than those bearing electron-
the generality of the organocatalyst/DBU-catalyzed withdrawing groups (Table 3, entries 4j and 4k). To expand the
cycloaddition reaction. The para-substituted aryl amines with applicability of this method, naphthalen-1-amine 3l was
electron-withdrawing groups (Table 3, entries 4e-h) showed submitted to the optimized reaction conditions to provide the
higher reactivity than those with electron-donating groups 89% yield (Table 3, 4l).
(Table 3, entries 4b-d). The reactivity of meta-substituted aryl Subsequently, the generality of cycloaddition of a series of
amines were also tested, and the corresponding products were terminal epoxides was investigated. First, the reaction of
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terminal epoxides with aliphatic groups, aniline, and CO2 was in excellent yield (please see data in parentheses in Table 3
View Article Online
DOI: 10.1039/C9OB00224C
performed, and good product yields were obtained (Table 3, correspond to the isolated yield of products).
entries 4m-p). However, the reaction of terminal epoxides with In order to clarify the function between organocatalysts and
aromatic substituents, aniline, and CO2 is difficult to produce DBU in every catalytic process, we conducted control
targeted products, excellent product yields were also achieved experiments by using the two component substrates in
by increasing reaction temperature to 110 °C (Table 3, entries different catalytic process (Figure 2). A quantitative yield of
4q-t). The heterocyclic amine of 2-aminopyridine was also cyclic carbonate was achieved in the cycloaddition between PO
investigated in this catalytic system. 2-Aminopyridine smoothly and CO2 only using 1e as catalyst, however, only a 10% yield was
reacted with PO and CO2 to give 75% of yield (Table 3, 4u). The obtained using DBU in the absence of 1e, which suggested that
alkylamine of n-pentylamine was also explored. However, no the DBU was not an essentially active species in the reaction of
desired product was obtained (Table 3, entry 4v). GC-MS PO with CO2 (Figure 2, eq 1). The reaction of PO with aniline
analysis showed that the reaction of n-pentylamine with PO is showed that neither organocatalyst 1e nor DBU played an
difficult to occur, which is responsible for the poor results. important role in the transformation, and the combination of
These results indicated this catalytic system is limited to 1e as catalyst and DBU as cocatalyst was demonstrated to be a
aromatic amines.
highly efficient catalyst system (Figure 2, eq 2). The reaction
Because the limitation of the low boiling point of propylene between above resulting cyclic carbonate and -amino alcohol
oxide, the scope of aryl amines was not evaluated. The proceeded smoothly catalyzed by DBU in the absence of 1e. This
substrate scope of epoxides was investigated as shown in Table observation evidently demonstrated that DBU was only
3. Under atmospheric pressure of CO2 and 90 °C, various catalytic species in this reaction (Figure 2, eq 3).
epoxides smoothly reacted with aniline to the desired products
H2N
O
O
+
CO2
45%
DBU, yield
0.4 mmol
10%
DBU, yield
0.4 mmol
+
10 mmol
90 oC
5 bar
10 mmol
2 mmol
90 oC
1e
53%
, yield
1e
99%
, yield
0.05 mmol
0.05 mmol
H
O
N
1e
99%
+DBU, yield
1e
99%
+DBU, yield
OH
O
0.05 mmol+0.4 mmol
0.05 mmol+0.4 mmol
O
(2)
(1)
DBU (0.4 mmol)
yield 93%
yield 97%
O
O
H
90 oC
O
DBU (0.4 mmol)
N
N
OH
(3)
O
+
1e
O
(0.05 mmol)
1e
(0.05 mmol)
no reaction
Figure 2 Control experiments for the reaction pathway.
According to the reports of the literature, the formation of the 2. The cyclic carbonate reacted also with aniline to afford the β-
intermediate -amino alcohol underwent two possible reaction amino alcohol as shown in Figure 3. Figure 2, eq 2 indicates that
pathways. To determine how the β-amino alcohol was PO reacted with aniline to generate the β-amino alcohol,
generated under our catalytic condition, two control however, the pathway based on the reaction of cyclic carbonate
experiments were performed to investigate the real reaction with aniline can be rule out as shown in Figure 3.
pathway. The β-amino alcohol could be formed through the
reaction between epoxides and aniline as shown in Figure 2, eq
4 | J. Name., 2012, 00, 1-3
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acids plays a role of a proton transfer agent.18 CVyicewleAr1ticlienOtnhlinies
work is consistent with the previous worDkO(FI:i1g0u.1r0e369/)C. 9OB00224C
DBU (0.4 mmol)
DBU (0.4 mmol)
O
trace
O
10 mmol
O
H
90 oC
N
OH
HO
O
+
HO
O
H2N
N
I
N
N
H
N
I
N
N
H
2 mmol
trace
N
N
1e
(0.05 mmol)
Figure 3 Investigation of possible reaction pathway.
1h
1e
In order to prove the function of the proton in the C2 position
of the imidazolium ring with the catalyst 1e in cycle 2 and cycle
3 in Figure 5, a catalyst 1h (Figure 4) was designed by
introducing a methyl group to the C2 position of the catalyst 1e.
The catalyst 1e can be transferred to NHC (N-heterocyclic
carbene) by the release of a molecule HI in the presence of DBU,
but the catalyst 1h cannot produce the NHC under the same
reaction condition. To explore the function of NHC in cycle 1, PO
and CO2 were selected as model substrates to investigate the
whether or not the NHC is involved in this reaction using the
catalysts 1e and 1h, respectively (Figure 4, eq 4). The proton in
the C2 position of the imidazolium ring was needed for a high
yield of cyclic carbonate, because the absence of proton
resulted in an obvious decrease in the yield of cyclic carbonate
from 99% to 79% (Figure 4, eq 4), which might be explained by
NHC is difficult to produce because the absence of the proton
in the C2 position of the imidazolium ring with the catalyst 1e.
In cycle 2, both the NHC and iodine anion can be used as
nucleophilic reagents. In order to prove the nucleophilic attack
to epoxide occurs whether in the NHC or iodine anion, PO and
aniline were selected as model substrates to investigate the
whether or not the NHC is involved in this reaction using the
catalysts 1e and 1h, respectively (Figure 4, eq 5). The results
showed that the iodine anion preferentially nucleophilic attack
to epoxide in the reaction of PO with aniline.
DBU (0.4 mmol)
1e
yield 99%
O
O
(0.05 mmol)
90 oC
10 mmol
+
CO2
O
O
(4)
DBU (0.4 mmol)
1h
5 bar
yield 79%
yield 99%
(0.05 mmol)
DBU (0.4 mmol)
1e
O
(0.05 mmol)
10 mmol
+
H
N
90 oC
OH (5)
H2N
DBU (0.4 mmol)
1h
yield 96%
2 mmol
(0.05 mmol)
Figure 4 Investigation of function of NHC (N-heterocyclic
carbene) in cycle 1 and cycle 2.
DBU (0.4 mmol)
1e
O
yield 99%
(0.05 mmol)
Since the NHC is not involved in the nucleophilic attack of
epoxide, nucleophilic activation may be done by the iodine
anion. If the halide anions play an important role of the
nucleophilic attack of epoxide, the halide anions have different
catalytic performance in the reaction of epoxide with aniline.
Therefore, the effect of halide anion bearing catalysts in the
reaction of PO with aniline was investigated in Figure 5. As
shown in Figure 5, the activity order of anion is I− > Br− > Cl−. It
well-known that Cl− has the highest nucleophilicity, whereas I−
has the strongest leaving ability. The results showed that the
leaving ability of halide anion is responsible for the reaction of
epoxide with aniline.
Supported by these control experiments, we propose the
mechanism of 1e/DBU-catalyzed the three component reaction
of CO2, aniline, and epoxides in Figure 6. In the case of
previously reported multifunctional organocatalyzed the
cycloaddition of CO2 with epoxides, it has been revealed that
the intramolecular synergistic activation mechanism was
realized, in which the in situ generated the carbene could
activate CO2, simultaneously the carboxyl group bearing amino
10 mmol
+
-amino alcohol
90 oC DBU (0.4 mmol)
1f
yield 73%
(0.05 mmol)
H2N
DBU (0.4 mmol)
1g
yield 67%
2 mmol
(0.05 mmol)
Figure 5 Effect of halide anion in the reaction of PO with aniline.
The observation from control experiments (Figure 2, eq 2)
disclosed the synergistic activation between catalyst 1e and
DBU in cycle 2. First, the carboxyl group of catalyst 1e activates
the C-O bond of epoxide through hydrogen bonding. In turn,
nucleophilic attack of the iodide anion to the sterically less
hindered carbon atom of the epoxide resulted in epoxide ring
opening. The aniline is activated by DBU through hydrogen
bonding, which resulted in the polarization of the N-H bond.
Next, the negatively charged nitrogen atom of the aniline
nucleophilically attacks the carbon atom of the ring opening
intermediate  to form the -amino alcohol.
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In cycle 3, hydroxyl groups bearing the -amino alcohol could synthesis of 3-aryl-2-oxazolidinones throughViewthAerticletOhnrleinee
be activated through DBU, then nucleophilically attacks the component reaction between CO2, aryl DaOmI:in10e.s10, 3a9n/Cd9eOpBo0x0i2d2e4sC.
carbonyl group of the cyclic carbonate resulting from cycle 1, The binary organocatalytic system was found to be robust for a
which further occurs a subsequent intermolecular proton series of terminal epoxides and applicable to various aryl
transfer process to afford intermediate . Second, amino group amines under relatively mild condition. In addition, the catalytic
with intermediate  could intramolecular coordinate to oxygen behavior of organocatalysts/DBU has been identified by control
of ester group through hydrogen bonding, which resulted in the experiments. In cycle 1, only organocatalysts were necessary for
polarization of the C-O bond. Subsequently, a nucleophilically the cycloaddition reaction of epoxides with CO2. In cycle 2, the
attack from nitrogen atom to carbon atom of carbonyl group reaction of epoxides with aryl amines was realized by the
with the intermediate , thereby forming the targeted product synergistic activation between organocatalysts and DBU. In the
and the diol byproduct.
final cycle, DBU without organocatalysts could activate the
In summary, the multifunctional organocatalysts in reaction between the -amino alcohol and the cyclic carbonate.
combination with DBU displayed high catalytic activity for the
R
O
OH
nPr
N
O
O
OH
H
N
N
N
O
R
O
O
1e
N
N
N
H
OH
R
O
H
N
O
nPr
O
nPr
O
nPr
H
I
N
O
O
N
O
N
O
HO
H
Cycle 1
H
O
N
N
N
O
N
N
R
O
R
PhNH2
+
DBU
Cycle 2
OH
nPr
1e
OH
H
N
HO
H
DBU
H
N
N
N
N
O
O
R
1e
R
O
H
N
CO2
O
I
O
O

H
N
-HI
DBU
R
OH
1e
N
O
OH
+
HO
N
O
R
R
HO
Cycle 3
R
H
N
O
R
O
HO
O
O
O
H
R
O
R
N


Figure 6 Proposed reaction mechanism.
Epoxides (2.0 mL), aryl amines (2.0 mmol), organocatalyst (0.05
mmol), and DBU (0.4 mmol) were introduced into a 25 mL
stainless steel autoclave that was equipped with a magnetic
stirrer. The reactor was pressurized with CO2 to 5 bar and then
heated at 90 °C for the required time. The reactor was cooled
to room temperature after the reaction. The reaction mixtures
Experimental
General procedure for synthesis of 3-aryl-2-oxazolidinones.
6 | J. Name., 2012, 00, 1-3
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were added to brine (15 mL) and extracted three times with 20.79; IR (KBr): 1741 cm-1 (C=O); Elemental analysis: calcd for
View Article Online
dichloromethane (3 × 15 mL). The solvent was removed under C10H10ClNO2: C 56.75, H 4.76, N 6.62; foundDCO5I5: 1.706.1,0H394/C.499O,BN0062.6294.C
reduced pressure, and the products were isolated by flash
chromatography.
Characterization data for 3-aryl-2-oxazolidinones.
3-(4-bromophenyl)-5-methyloxazolidin-2-one (4g).3g Purification by
flash chromatography (petroleum ether/EtOAc = 3:1) gave a white
solid (508 mg, 99%); 1H NMR (400 MHz, CDCl3) δ 7.48-7.40 (m, 4 H),
5-methyl-3-phenyloxazolidin-2-one (4a).3g Purification by flash 4.82-4.74 (m, 1H), 4.07 (d, J = 4.4 Hz, 1 H), 3.58 (dd, J = 8.4, 6.8 Hz, 1
chromatography (petroleum ether/EtOAc = 5:1) gave a white solid H), 1.53 (d, J =6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 154.72, 137.60,
1
(337 mg, 95%); H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 7.6 Hz, 2H), 132.02, 119.69, 116.76, 69.70, 51.79, 20.76; IR (KBr): 1737 cm-1
7.36 (t, J = 8.8 Hz, 2H), 7.12 (t, J = 7.6 Hz, 1H), 4.81-4.72 (m, 1H), 4.10 (C=O); Elemental analysis: calcd for C10H10BrNO2: C 46.90, H 3.94, N
(t, J = 8.6 Hz, 1H), 3.60 (dd, J = 8.0, 7.2 Hz, 1H), 1.51 (d, J = 6.6 Hz, 3H); 5.47; found C 46.21, H 3.75, N 5.61.
13C NMR (100 MHz, CDCl3) δ 154.98, 138.50, 129.12, 124.02, 118.27,
3-(4-iodophenyl)-5-methyloxazolidin-2-one (4h).9b Purification by
69.63, 51.97, 20.80; IR (KBr): 1754 cm-1 (C=O); Elemental analysis:
flash chromatography (petroleum ether/EtOAc = 5:1) gave a white
calcd for C10H11NO2: C 67.78, H 6.26, N 7.90; found C 67.97, H 6.38, N
8.01.
solid (602 mg, 99%); 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 8.4 Hz,
2H) 7.30 (d, J = 8.8 Hz, 2H), 4.80-4.75 (m, 1H), 4.08 (t, J = 8.6 Hz, 1H),
5-methyl-3-(p-tolyl)oxazolidin-2-one (4b).3g Purification by flash 3.57 (d, J = 8.0 Hz, 1H), 1.52 (d, J = 6.4 Hz, 3H); 13C NMR (100 MHz,
chromatography (petroleum ether/EtOAc = 2:1) gave a white solid CDCl3) δ 154.66, 138.31, 137.96, 119.99, 87.34, 69.70, 51.68, 20.78;
(326 mg, 85%); 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.8 Hz, 2 H), IR (KBr): 1745 cm-1 (C=O); Elemental analysis: calcd for C10H10INO2: C
7.16 (d, J = 8.4 Hz 2H), 4.78-4.70 (m, 1H), 4.08 (t, J =7.6 Hz, 1H), 3.58 39.63, H 3.33, N 4.62; found C 40.12, H 3.46, N 4.75.
(dd, J = 8.8, 7.2 Hz, 1H), 2.30 (s, 3H) 1.50 (d, J =6.4 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 155.35, 136.28, 133.92, 129.90, 118.64, 69.88,
52.39, 21.07; IR (KBr): 1745 cm-1 (C=O); Elemental analysis: calcd for
5-methyl-3-(m-tolyl)oxazolidin-2-one (4i).20 Purification by flash
chromatography (petroleum ether/EtOAc = 5:1) gave a yellow oil
(288 mg, 75%); 1H NMR (400 MHz, CDCl3) δ 7.38 (s, 1H), 7.31-7.23
C11H13NO2: C 69.09, H 6.85, N 7.32; found C 69.75, H 6.32, N 7.52.
(m, 2H), 6.96 (d, J = 7.6 Hz, 1H), 4.81-4.73 (m, 1H), 4.10 (t, J = 8.4 Hz,
3-(4-methoxyphenyl)-5-methyloxazolidin-2-one (4c).3g Purification 1H), 3.63-3.59 (m, 1H), 2.37 (s, 3H), 1.53 (d, J = 6.0 Hz, 3H). 13C NMR
by flash chromatography (petroleum ether/EtOAc = 2:1) gave a white (101 MHz, CDCl3-d) δ 155.02, 139.11, 138.47, 128.96, 124.93, 119.10,
oil (316 mg, 87%); 1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 8.8 Hz, 2) 115.44, 69.61, 52.15, 21.75, 20.83; IR (CH2Cl2): 1750 cm-1 (C=O);
6.87 (d, J = 9.2 Hz, 2H), 4.75-4.70 (m, 1H), 4.04 (t, J = 8.4 Hz, 1H), 3.77 Elemental analysis: calcd for C11H13NO2: C 69.09, H 6.85, N 7.32;
(s, 3H), 3.55 (dd, J = 12.4, 7.2 Hz, 1H), 1.49 (d, J = 6.0 Hz, 3H); 13C NMR found C 69.58, H 6.62, N 7.59.
(100 MHz, CDCl3) δ 156.24, 155.19, 131.62, 120.15, 114.23, 69.53,
5-methyl-3-(3-nitrophenyl)oxazolidin-2-one (4j).20 Purification by
55.50, 52.36, 20.68; IR (CH2Cl2): 1741 cm-1 (C=O); Elemental analysis:
calcd for C11H13NO3: C 63.76, H 6.32, N 6.76; found C 64.31, H 6.79, N
6.83.
flash chromatography (petroleum ether/EtOAc = 2:1) gave a yellow
solid (405 mg, 91%); 1H NMR (400 MHz, CDCl3) 8.20 (t, J = 2.2 Hz,1H)
δ 8.13-8.10 (m, 1H), 7.98-7.95 (m, 1H), 7.55 (t, J = 8.4 Hz, 1H), 4.90-
3-(4-ethoxyphenyl)-5-methyloxazolidin-2-one (4d).19 Purification by 4.82 (m, 1H), 4.20 (t, J = 8.4 Hz,1H), 3.70 (dd, J = 8.4, 6.8Hz, 1H), 1.58
flash chromatography (petroleum ether/EtOAc = 5:1) gave a white (d, J = 6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 154.60, 148.73, 139.71,
1
solid (412 mg, 93%); H NMR (400 MHz, CDCl3) δ 7.42-7.38 (m, 2H), 130.10, 123.97, 118.51, 112.33, 70.04, 51.77, 20.80; IR (KBr): 1754
6.90-6.86 (m, 2H), 4.79-4.71 (m, 1H), 4.08-3.98 (m, 3H), 3.57 (dd, J = cm-1 (C=O); Elemental analysis: calcd for C10H10N2O4: C 54.05, H 4.54,
7.2, 8.8 Hz, 1H), 1.50 (d, J = 7.2 Hz, 3H), 1.40 (t, J = 3.0 Hz, 3H); 13C N 12.61; found C 54.39, H 4.73, N 12.95.
NMR(100 MHz, CDCl3) δ 155.78, 155.35, 131.64, 120.30, 115.02,
3-(3,5-dichlorophenyl)-5-methyloxazolidin-2-one (4k). Purification
69.65, 63.88, 52.55, 20.86, 14.98; IR (KBr): 1741 cm-1 (C=O);
by flash chromatography (petroleum ether/EtOAc = 5:1) gave a white
Elemental analysis: calcd for C12H15NO3: C 65.14, H 6.83, N 6.33;
found C 65.83, H 7.05, N 6.67.
solid (488 mg, 99%); 1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 2.0 Hz,
2H), 7.11 (t, J = 1.8Hz, 1H), 4.85-4.77 (m, 1H), 4.10 (t, J = 8.4 Hz 1H),
3-(4-fluorophenyl)-5-methyloxazolidin-2-one (4e).3g Purification by 3.61 (dd, J = 7.2, 1.6 Hz, 1H), 1.55 (d, J = 6.4 Hz, 3H); 13C NMR (100
flash chromatography (petroleum ether/EtOAc = 3:1) gave a white MHz, CDCl3) δ 154.34, 140.33, 135.56, 123.87, 116.34, 69.89, 51.73,
solid (388 mg, 99%); 1H NMR (400 MHz, CDCl3) δ 7.49-7.44 (m, 2H), 20.79; IR (KBr): 1758 cm-1 (C=O); Elemental analysis: calcd for
7.07-7.01 (m, 2H), 4.80-4.72 (m, 1H), 4.07 (t, J = 8.4, 1H), 3.58 (dd, J C10H9Cl2NO2: C 48.81, H 3.69, N 5.69; found C 49.17, H 3.57, N 5.82;
= 8.8, 3.2 Hz, 1H), 1.50 (d, J =6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) HRMS (ESI) calcd for C10H9Cl2NO2 [M+Na]+ 267.9908, found 267.9898.
δ 160.49, 158.07, 155.09, 134.65, 120.10, 120.02, 115.90, 115.68,
5-methyl-3-(naphthalen-1-yl)oxazolidin-2-one (4l).3a Purification by
69.69, 52.23, 20.76. 19F NMR (376 MHz, CDCl3) δ -118.75; IR (KBr):
flash chromatography (petroleum ether/EtOAc = 2:1) gave a white
1741 cm-1 (C=O); Elemental analysis: calcd for C10H10FNO2: C 61.53, H
solid (406 mg, 89%); 1H NMR (400 MHz, CDCl3) δ 7.90-7.82 (m, 3H),
5.16, N 7.18; found C 61.65, H 4.96, N 7.36.
7.58-7.44 (m, 4H), 4.95-4.90 (m, 1H), 4.11 (t, J = 4.0 Hz, 1H), 3.62 (dd,
3-(4-chlorophenyl)-5-methyloxazolidin-2-one (4f).3g Purification by J = 6.0, 8.8 Hz, 1H), 1.60 (d, J = 8.8 Hz, 3H); 13C NMR(100 MHz, CDCl3)
flash chromatography (petroleum ether/EtOAc = 5:1) gave a white δ 157.10, 134.56, 134.02, 129.91, 128.60, 128.58, 126.90, 126.47,
solid (419 mg, 99%); 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 9.2 125.59, 124.50, 122.35, 70.84, 55.81, 20.65; IR (KBr): 1741 cm-1
Hz,2H), 7.32 (d, J = 8.8 Hz, 2H), 4.82-4.72 (m, 1H), 4.08 (t, J =8.4 Hz, (C=O); Elemental analysis: calcd for C14H13NO2: C 73.99, H 5.77, N
1H), 3.58 (dd, J = 6.8, 8.4 Hz, 1H), 1.52 (d, J = 6.8 Hz, 3H); 13C NMR(100 6.16; found C 74.86, H 5.93, N 6.34.
MHz, CDCl3) δ 154.81, 137.12, 129.22, 129.13, 119.40, 69.70, 51.90,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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5-ethyl-3-phenyloxazolidin-2-one (4m).3d Purification by flash cm-1 (C=O); Elemental analysis: calcd for C15H12FNO2: CV7ie0w.0A3rti,cHle O4n.7lin0e,
DOI: 10.1039/C9OB00224C
chromatography (petroleum ether/EtOAc = 2:1) gave a colorless oil N 5.44; found C 70.62, H 4.83, N 5.56.
(310 mg, 80%); 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.0 Hz, 2H ),
5-(4-chlorophenyl)-3-phenyloxazolidin-2-one (4s).14 Purification by
7.34 (t, J = 7.2 Hz, 2H), 7.10 (t, J = 8.0 Hz, 1H), 4.59-4.52 (m, 1H), 4.04
flash chromatography (petroleum ether/EtOAc = 5:1) gave a white
(t, J = 8.8 Hz, 1H), 3.62 (t, J = 8.0 Hz, 1H), 1.90-1.72 (m, 2H), 1.05 (t, J
solid (510 mg, 93%); 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.8 Hz,
= 7.6 Hz, 3H); 13C NMR(100 MHz, CDCl3) δ 154.93, 138.38, 128.96,
2H), 7.43-7.36 (m, 6H), 7.18-7.14 (m, 1H), 5.62 (t, J = 8.0 Hz, 1H), 4.39
123.82, 118.10, 74.13, 49.99, 27.95, 8.72; IR (CH2Cl2): 1754 cm-1
(C=O); Elemental analysis: calcd for C11H13NO2: C 69.09, H 6.85, N
7.32; found C 69.72, H 7.06, N 7.68.
(t, J = 8.4 Hz, 1H), 3.95-3.91 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
154.59, 138.11, 136.75, 135.23, 129.44, 129.30, 127.23, 124.49,
118.47, 73.48, 52.75; IR (KBr): 1762 cm-1 (C=O); Elemental analysis:
5-butyl-3-phenyloxazolidin-2-one (4n).3d Purification by flash calcd for C15H12ClNO2: C 65.82, H 4.42, N 5.12; found C 66.28, H 4.59,
chromatography (petroleum ether/EtOAc = 2:1) gave a white solid N 5.33.
(356 mg, 81%); 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 6.8 Hz, 2H),
7.38 (t, J = 8.0 Hz, 2H), 7.12 (t, J = 7.2 Hz, 1H), 4.66-4.59 (m, 1H), 4.07
(t, J = 8.8 Hz, 1H), 3.65 (d, J = 7.2 Hz, 1H), 1.89-1.81 (m, 1H), 1.77-1.68
5-(4-bromophenyl)-3-phenyloxazolidin-2-one (4t).14 Purification by
flash chromatography (petroleum ether/EtOAc = 5:1) gave a white
1
solid (500 mg, 91%); H NMR (400 MHz, CDCl3) δ 7.58-7.53 (m, 4H),
(m, 1H), 1.55-1.49 (m, 1H), 1.43-1.38 (m, 3H), 0.94 (t, J = 8.0 Hz, 3H);
7.39 (t, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.16 (t, J = 8.0 Hz, 1H),
5.61 (t, J = 8.0 Hz, 1H), 4.39 (t, J = 8.8 Hz, 1H), 3.92 (m, 1H); 13C NMR
(100 MHz, CDCl3) δ 154.45, 137.96, 137.16, 132.25, 129.17, 127.36,
124.37, 123.19, 118.35, 73.37, 52.56; Elemental analysis: calcd for
13C NMR(100 MHz, CDCl3) δ 155.13, 138.61, 129.21, 124.09, 118.34,
73.27, 50.69, 34.92, 26.83, 22.57, 14.10; IR (KBr): 1745 cm-1 (C=O);
Elemental analysis: calcd for C13H17NO2: C 71.21, H 7.81, N 6.39;
found C 71.76, H 8.15, N 6.61.
C15H12BrNO2: C 56.63, H 3.80, N 4.40; found C 56.54, H 3.81, N 4.56.
5-(butoxymethyl)-3-phenyloxazolidin-2-one (4o).20 Purification by
5-methyl-3-(pyridin-2-yl)oxazolidin-2-one (4u).3a Purification by flash
flash chromatography (petroleum ether/EtOAc = 2:1) gave a
chromatography (petroleum ether/EtOAc = 5:1) gave a white solid
colorless oil (435 mg, 87%); 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J
1
(273 mg, 75%); H NMR (400 MHz, CDCl3) δ 8.31-8.29 (m, 1H), 8.21
=8.4 Hz, 2H), 7.32 (t, J = 8.8 Hz, 2H), 7.08 (t, J = 6.4 Hz, 1H), 4.71-4.65
(d, J = 8.0 Hz, 1H), 7.71-7.66 (m, 1H), 7.03-7.00 (m, 1H), 4.84-4.76 (m,
(m, 1H), 3.99 (t, J = 8.8 Hz, 1H), 3.87 (t, J = 8.8 Hz, 1H), 3.62 (d, J =
1H), 4.35 (t, J = 8.6 Hz, 1H), 3.82 (dd, J = 10.4, 7.6 Hz, 1H), 1.52 (d, J =
3.2Hz, 2H), 3.48 (t, J = 6.4Hz, 2H), 1.55-1.48 (m, 2H), 1.34-1.29 (m,
6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 154.59, 150.97, 147.44,
2H), 0.87 (t, J = 7.2 Hz, 3H); 13C NMR(100 MHz, CDCl3) δ 154.65,
137.68, 118.91, 112.92, 70.32, 50.68, 20.65; Elemental analysis: calcd
for C9H10N2O2: C 60.66, H 5.66, N 15.72; found C 60.87, H 5.72, N
15.98.
138.31, 128.94, 123.83, 118.12, 71.74, 71.41, 70.75, 47.12, 31.55,
19.13, 13.81; IR (CH2Cl2): 1741 cm-1 (C=O);Elemental analysis: calcd
for C14H19NO3: C 67.45, H 7.68, N 5.62; found C 68.25, H 7.83, N 5.77.
5-((allyloxy)methyl)-3-phenyloxazolidin-2-one (4p).3g Purification by
flash chromatography (petroleum ether/EtOAc = 2:1) gave a
colorless oil (397 mg, 85%); 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J
Conflicts of interest
The authors declare no competing financial interest.
=8.8 Hz, 2H), 7.36 (t, J =8.0 Hz, 2H), 7.12 (t, J =7.2 Hz, 1H), 5.93-5.82
(m, 1H), 5.30-5.18 (m, 2H), 4.78-4.72 (m, 1H), 4.07-4.03 (m, 3H), 3.94
(dd, J =6.0, 8.8 Hz, 1H), 3.69 (d, J =7.2 Hz, 2H); 13C NMR(100 MHz,
Acknowledgements
CDCl3) δ 154.70, 138.37, 134.03, 129.13, 124.08, 118.28, 117.87,
We are grateful for the support from the National Natural
72.75, 71.36, 70.14, 47.34; IR (CH2Cl2): 1750 cm-1 (C=O); Elemental
Science Foundation of China (Grant No. 21868033).
analysis: calcd for C13H15NO3: C 66.94, H 6.48, N 6.00; found C 67.39,
H 6.76, N 6.28.
3,5-diphenyloxazolidin-2-one (4q).14 Purification by flash
chromatography (petroleum ether/EtOAc = 2:1) gave a white solid
(326 mg, 85%); 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.8 Hz, 2H),
7.44-7.36 (m, 7H), 7.15 (t, J = 7.6 Hz, 1H), 5.65-5.60 (m, 1H), 4.40-4.35
(m, 1H), 3.98-3.93 (m, 1H); 13C NMR(100 MHz, CDCl3) δ 154.81,
138.26, 138.23, 129.23, 129.16, 125.80, 124.30, 118.42, 74.15, 52.82;
IR (KBr): 1750 cm-1 (C=O); Elemental analysis: calcd for C15H13NO2: C
75.30, H 5.48, N 5.85; found C 74.88, H 5.23, N 6.01.
Notes and references
1
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5-(4-fluorophenyl)-3-phenyloxazolidin-2-one (4r).14 Purification by
flash chromatography (petroleum ether/EtOAc = 5:1) gave a white
solid (506 mg, 98%); 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 8.4 Hz,
2H), 7.44-7.37 (m, 4H), 7.18-7.10 (m, 3H), 5.62 (t, J =8.0 Hz, 1H), 4.38
(t, J = 8.4 Hz, 1H), 3.96-3.92 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
164.44, 161.97, 154.64, 138.17, 134.05, 134.01, 129.29, 127.89,
127.81, 124.44, 118.46, 116.35, 116.13, 76.63, 52.86; IR (KBr): 1745
8 | J. Name., 2012, 00, 1-3
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