Thermodynamically favorable synthesis of 2-oxazolidinones through silver-catalyzed reaction of propargylic alcohols, CO2, and 2-aminoethanols

Article abstract of DOI:10.1002/cssc.201600470

Development of catalytic routes to incorporate CO₂ into carbonyl compounds at mild conditions remains attractive and challenging. Herein, a one-pot three-component cascade reaction of terminal propargylic alcohols, CO₂, and 2-aminoethanols through Ag^I-based catalysis is reported for the synthesis of carbonyl compounds through C—O/C—N bond formation. This thermodynamically favorable route can be ingeniously regulated to afford a wide range of 2-oxazolidinones along with concurrent production of α-hydroxyl ketone derivatives in excellent yields and selectivity. Preliminary mechanistic studies indicate that such a process proceeds through successive formation of α-alkylidene cyclic carbonate, β-oxopropylcarbamate, and 2-oxazolidinones.

Full text of DOI:10.1002/cssc.201600470

DOI: 10.1002/cssc.201600470
Communications
Thermodynamically Favorable Synthesis of 2-
Oxazolidinones through Silver-Catalyzed Reaction of
Propargylic Alcohols, CO2, and 2-Aminoethanols
Qing-Wen Song,[a, c] Zhi-Hua Zhou,[a] Mei-Yan Wang,[a] Kan Zhang,[c] Ping Liu,[c] Jia-Yao Xun,[c]
and Liang-Nian He*[a, b]
Development of catalytic routes to incorporate CO2 into car-
bonyl compounds at mild conditions remains attractive and
challenging. Herein, a one-pot three-component cascade reac-
tion of terminal propargylic alcohols, CO2, and 2-aminoethanols
through AgI-based catalysis is reported for the synthesis of car-
bonyl compounds through CÀO/CÀN bond formation. This
thermodynamically favorable route can be ingeniously regulat-
ed to afford a wide range of 2-oxazolidinones along with con-
current production of a-hydroxyl ketone derivatives in excel-
lent yields and selectivity. Preliminary mechanistic studies indi-
cate that such a process proceeds through successive forma-
tion of a-alkylidene cyclic carbonate, b-oxopropylcarbamate,
and 2-oxazolidinones.
amines and CO2,[6] three-component reaction of propargylic al-
cohols, primary amines, and CO2,[7] condensation of amino al-
cohols and CO2,[8] and other convenient paths.[9] Although con-
siderable progress has been made, the exploration of effective
and economical catalytic processes using CO2 as a feedstock
under mild reaction conditions could be still highly desirable;
this represent a significant and challenging area in both cataly-
sis and sustainable chemistry.
b-Oxopropylcarbamate[10] and 1,3-oxazolidin-2-one[3–5] motifs
are widely available compounds in synthetic and pharmaceuti-
cal chemistry. Generally, they are prepared through the reac-
tion of propargylic alcohols, aliphatic amines, and CO2
(Scheme 1a, b). Notably, the formation of b-oxopropylcarba-
mate and oxazolidinone scaffolds depends on the structure of
the amine (primary[7] and secondary[10]) employed. Considering
the attractiveness of effective and convenient routes, we
became interested in developing an alternative efficacious
methodology for the conversion of CO2 into more valuable
chemicals using dual nucleophilic reagents. In this context, we
hypothesized that a hydroxyl group as the second nucleophilic
species can be attached to the reactive b-oxopropylcarbamate
intermediate through a three-component reaction leading to
Carbon dioxide, representing an abundant, safe, easily avail-
able, and renewable carbon resource, is attractive as an envi-
ronmentally friendly feedstock for manufacturing commodity
chemicals, fuels, and materials.[1] In commercial processes,
chemical utilization of CO2 as green carbonyl source is of great
significance as an alternative to the CO and phosgene process
for the synthesis of value-added products, such as carbonates,
polycarbonates, polyurethanes, urea, and urethane through CÀ simultaneous generation of two types of carbonyl compounds
O and CÀN bond formation.[2] In this respect, 2-oxazolidinones,
among the most important heterocyclic compounds, are play-
ing a significant role as chemical intermediates[3] and chiral
auxiliaries[4] in organic synthesis and as antibacterial drugs[5] in
pharmaceutical chemistry. In recent years, many environmen-
tally benign synthetic processes attracted considerable atten-
tion to provide better methods for the synthesis of various ox-
azolidinones, such as carboxylative cyclization of propargylic
(Scheme 1c). As part of our continuing studies on CO2 chemis-
try associated with propargylic alcohols,[7d,10d] we herein pres-
ent an unprecedented thermodynamically favored (DG=
À22.39 kcalmolÀ1 <0; for detailed DFT calculation see the Sup-
porting Information, Tables S1 and S2) one-pot process to syn-
thesize 2-oxazolidinones and a-hydroxyl ketones[11] from termi-
nal propargylic alcohols, CO2, and 2-aminoethanols. As a result,
the thermodynamic limitation of the condensation reaction of
2-aminoalcohol and CO2 (DG=2.75 kcalmolÀ1 >0, see Table S1
and S2 in the Supporting Information) is circumvented by
avoiding the dehydration step.
[a] Dr. Q.-W. Song, Z.-H. Zhou, M.-Y. Wang, Prof. L.-N. He
State Key Laboratory and Institute of Elemento-Organic Chemistry
Nankai University
To begin with, the individual reaction of 2-(benzylamino)-
ethanol (1a) and a-alkylidene cyclic carbonate (IM-a) was per-
formed to identify the catalytic conditions to realize the goal
(Table 1). We initially focused on silver compounds as catalyst
due to their high activity towards various alkynes.[12]
Tianjin, 300071 (P.R. China)
E-mail: heln@nankai.edu.cn
[b] Prof. L.-N. He
Collaborative Innovation Center of Chemical Science and Engineering
Nankai University
The reaction of 1a and IM-a did not occur for 2 h in the ab-
sence of any catalyst at room temperature (Table 1, entry 1). A
relatively high temperature or Ag catalyst rendered the reac-
tion to give the b-oxopropylcarbamate intermediate IM-b (en-
tries 2 and 3, 608C), presumably because the nucleophilicity of
the amine species in IM-a is reduced by the formation of hy-
drogen bonds through strong interaction between the hydrox-
Tianjin, 300071 (P.R. China)
[c] Dr. Q.-W. Song, K. Zhang, Dr. P. Liu, J.-Y. Xun
State Key Laboratory of Coal Conversion
Institute of Coal Chemistry
Chinese Academy of Sciences
Taiyuan, 030001 (P. R. China)
Supporting Information for this article can be found under:
http://dx.doi.org/10.1002/cssc.201600470.
ChemSusChem 2016, 9, 1 – 6
1
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

Communications
Scheme 1. CO2 conversion with propargylic alcohols and amines. Path a: the reaction of propargylic alcohols, CO2, and secondary amines to afford b-oxopro-
pylcarbamates; path b: the reaction of propargylic alcohols, CO2, and primary amines to form vinyl oxazolidinones; path c: three-component cascade reaction
of terminal propargylic alcohols, CO2, and 2-aminoethanols.
Table 1. Stepwise synthesis trials.[a]
Table 2. Optimization of the reaction conditions.[a]
Entry
Ag catalyst
Additive
Yield[b] [%]
IM-b
3a
4a
1[c]
2
3
4
5[d]
–
–
–
–
–
PPh3
PPh3
0
47
49
94
46
0
0
1
5
30
0
0
1
5
29
Ag2CO3
Ag2CO3
Ag2CO3
[a] Reaction conditions: 1a (75.6 mg, 0.5 mmol), IM-a (64.0 mg,
0.5 mmol), Ag2CO3 (10 mol%), PPh3 (40 mol%), CHCl3 (1 mL), 608C, 2 h,
yields of IM-b, 3a and 4a are related to 1a. [b] Determined by 1H NMR
spectroscopy using 1,1,2,2-tetrachloroethane as the internal standard.
[c] 258C. [d] 24 h.
Entry
Catalyst
Additive
Solvent
Yield [%]
3a[b]
4a[b]
1
2
3
4
5
6
7
8
AgCl
AgBF4
AgNO3
AgOAc
Ag2O
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
–
L1
L2
PCy3
L3
L4
L5
L6
DBU
2,2’-Bipy
L5
L5
L5
L5
L5
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CHCl3
1
2
6
11
10
17
0
0
9
12
1
7
22
9
14
0
37
17
0
64
77
92
1
2
6
10
10
16
0
0
8
11
1
6
22
9
14
0
35
15
0
62
76
90
1
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
yl and amino groups, which was supported by a H NMR study
(Supporting Information, Figure S1). Interestingly, a basic silver
complex, for example Ag2CO3/PPh3, allowed the reaction to
proceed further to form 3-benzyloxazolidin-2-one (3a) and 3-
hydroxy-3-methylbutan-2-one (4a) (entries 4, 5). On the other
hand, we also found that the bifunctional Ag2CO3/PPh3 system
promoted the carboxylative cyclization of propargylic alcohols
with CO2 to afford a-alkylidene cyclic carbonates.[10d]
9
10
11
12
13
14
15
16
17
18
19
20[c]
21[c,d]
22[c,d,e]
Encouraged by these results, we then continued our studies
by exploring the simultaneous formation of 3a and 4a from
1a and 2-methylbut-3-yn-2-ol (2a) with CO2 under 1 MPa CO2
at 608C for 12 h (Table 2). Several representative silver com-
pounds as p-Lewis acid capable of activating CÀC triple bond
were primarily screened (entries 1–6). Silver compounds such
as AgOAc, Ag2O, and Ag2CO3 with stronger alkalinity displayed
a slightly higher activity than AgCl, AgBF4, and AgNO3 under
otherwise identical conditions (entries 4–6 vs 1–3). Particularly,
the Ag2CO3/PPh3 system gave the best result with a 17% yield
of 3a as well as 16% yield of a-hydroxyl ketone 4a (entry 6).
On the other hand, Ag2CO3 itself was found to be ineffective
CH2Cl2
DMF
CHCl3
CHCl3
CHCl3
L5
[a] Unless otherwise specified, all the reactions were performed with 1a
(75.6 mg, 0.5 mmol), 2a (42.1 mg, 1 equiv.), [Ag+] (5 mol%), additive
(10 mol%), CO2 (1 MPa), 608C, solvent (1 mL), 12 h, yields of 3a and 4a
are related to 1a. [b] Determined by H NMR analysis by using 1,1,2,2-tet-
rachloroethane as an internal standard. [c] Ag2CO3 (5 mol%). [d] 2a
1
(63.2 mg, 1.5 equiv.). [e] 18 h.
&
ChemSusChem 2016, 9, 1 – 6
www.chemsuschem.org
2
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Communications
(entry 7), suggesting
a [(PPh3)2Ag]2CO3-catalyzed process,
Table 3. Substrate scope.[a]
which was verified in previous studies.[10d,13]
To promote the catalytic efficiency, several typical additives
in Table 2 including monophosphine {such as tri(furan-2-yl)-
phosphine (L1), 2-[2-(diphenylphosphino)ethyl]pyridine (L2),
tricyclohexylphosphine (PCy3)} and bidentate phosphine li-
gands[(e.g., 1,2-bis(diphenylphosphanyl)benzene (Dppbz, L3);
1,3-bis(diphenylphosphino)propane (Dppp, L4); 4,5-bis(diphe-
nylphosphino)-9,9-dimethylxanthene (Xantphos, L5); 1,1’-bis(di-
phenylphosphino)ferrocene (Dppf, L6)] were evaluated (en-
tries 8–14). Especially, bidentate phosphine L5 was found to
the best and gave the desired product 3a in 22% yield
(entry 13). As seen from entry 15, a N-containing organic base
(e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)] was also effec-
tive with a slightly lower efficiency than PPh3 (entry 15 vs. 6).
However, 2,2’-bipyridine (2,2’-Bipy) showed no activity
(entry 16). Moreover, various reaction conditions involving the
solvent, 2a loading, and reaction time were also examined in
the presence of ligand L5 (entries 17–22). As illustrated by the
results, the solvent effect is conspicuous, probably acting on
the stability of the active silver complex. Clearly, using CHCl3 as
solvent gave the most promising result with 37% yield of 3a
(entry 17). Modulating the ratio of 1a to 2a and prolonging
the reaction time, excellent results were obtained (entries 21,
22).
Entry
Product 3
Product 4
Yield[b] [%]
3
4
1
2
3
4
5
X=H, 3a
R1 =R2 =Me, 4a
R1 =R2 =Me, 4a
R1 =R2 =Me, 4a
R1 =R2 =Me, 4a
R1 =R2 =Me, 4a
92(90[c])
91
90(85[c])
90
84
57
X=Me, 3b
X=MeO, 3c
X=Cl, 3d
X=NO2, 3e
84
57(70[c,d]
33(40[c,d]
)
)
31
6
R1 =R2 =Me, 4a
89
89
7
R1 =R2 =Me, 4a
73
71
8[e]
X=H, 3a
X=H, 3a
X=H, 3a
R1 =Me, R2 =Et, 4b
R1 =R2 =À(CH2)5À, 4c
R1 =Me, R2 =Ph, 4d
80
83
84
79
57
85
9[e]
10[e]
11
X =H, 3a
47[c]
47[c]
[a] Reactions were carried out with 0.5 mmol 1, 0.75 mmol 2, 5 mol%
Ag2CO3, 10 mol% L5 (5 mol%, relative to 1) under 1.0 MPa CO2 at 608C
in CHCl3 (1.0 mL) for 18 h, yields of 3 and 4 are related to 1. [b] Deter-
mined by 1H NMR analysis using 1,1,2,2-tetrachloroethane as an internal
standard. [c] Isolated yield. [d] 48 h. [e] 24 h.
With the suitable catalytic conditions in hand, we next ex-
plored the scope of the three-component reaction. As shown
in Table 3, the reactions of a wide range of aliphatic- and aro-
matic-substituted 2-aminoethanols proceeded smoothly.
Benzyl-substituted 2-aminoalcohols with electron-donating
group at the aromatic ring performed well, giving rise to the
desired products, that is, 2-oxazolinones (3) and a-hydroxyl ke-
tones (4), in high yields (entries 1–3). Nevertheless, benzyl-
substituted 2-aminoethanols with electron-withdrawing group
showed a slight reduction in reactivity, and an increased reac-
tion time was required for improved yield (entries 4, 5). Pre-
sumably, the electron-withdrawing chloro and nitro groups
could slow down the ammonolysis rate. Interestingly, bis(2-
ethanolamine), which was generally reported to exhibit poor
reactivity in the literature,[8c] was also successfully transformed
into ethoxy 2-oxazolidinone (3g) in 73% yield (entry 7). What
is more, propargylic alcohols 2b–2e with alkyl or phenyl sub-
stituents at the propargylic position were also effective, yield-
ing the corresponding 2-oxazolidinone 3a and a-hydroxyl ke-
tones 4b–4e in moderate to good yields (entries 8–11).
To obtain further insight into the reaction mechanism, we
also performed individual reactions of a-alkylidene cyclic car-
bonate with 2-aminoethanols. As seen from the results,
2-aminoethanol 1a reacted with a-alkylidene cyclic carbonate
IM-a smoothly to yield the desired product 2-oxazolidinone 3a
along with co-product a-hydroxyl ketone 4a [Eq. (2)]. Accord-
ingly, the synthesis likely occurs through a reaction sequence
of ammonolysis and subsequent intramolecular cyclization.
To confirm the reaction pathway, a two-component reaction
13
of
C -labeled a-alkylidene cyclic carbonate IM-a’ and 2-
carbonyl
aminoethanol 1a was run as shown in Equation (1). To our de-
light, b-oxopropylcarbamate IM-b’ was obtained in excellent
13
yield. The structure of
C -labeled IM-b’ was unambigu-
carbonyl
ously confirmed by 13C NMR spectroscopy and high-resolution
(HR)MS (Figures 1, S2, and S3). On the other hand, carbonyl
shift of the ketone part in IM-b was found to be 206.5 ppm in
the 13C NMR spectrum (Supporting Information). These results
support the ammonolysis pathway, being consistent with pre-
vious analogous mechanism of a-alkylidene cyclic carbonate
IM-a with amines.[7,10]
A plausible reaction mechanism is proposed (Scheme 2) on
the basis of the above results. The carboxylative cyclization of
propargylic alcohol 2 with CO2 initially affords the a-alkylidene
cyclic carbonate intermediate IM-A through silver catalysis,
which then proceeds via a nucleophilic ring-opening reaction
with the 2-aminoethanol to generate the corresponding b-oxo-
propylcarbamate IM-B. The hydroxyl group as nucleophilic
ChemSusChem 2016, 9, 1 – 6
www.chemsuschem.org
3
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

Communications
13
Figure 1. 13C NMR (top) analysis and HRMS (bottom) of the
C
-labeled intermediate.
carbonyl
Acknowledgements
This work was financially supported by the National
Natural Science Foundation of China, National key re-
search and development project (2016YFA0602900),
and the Foundation of State Key Laboratory of Coal
Conversion (Grant No. J16-17-902-2), Specialized Re-
search Fund for the Doctoral Program of Higher Educa-
tion (project 20130031110013), MOE Innovation Team
(IRT13022) of China and the “111” Project of Ministry of
Education of China (project No. B06005).
Scheme 2. Plausible reaction mechanism.
species in the intermediate IM-B can also be activated by the
basic silver complex. Subsequently, an intramolecular nucleo-
philic cyclization takes place to yield 2-oxazolidinone 3 and
concurrently form a-hydroxyl ketone 4.
Keywords: carbon dioxide fixation
homogeneous catalysis · multicomponent reaction · synthetic
methods
·
heterocycles
·
In summary, an unprecedented three-component protocol
using terminal propargylic alcohols, CO2, and 2-aminoethanols
through AgI catalysis was established for the efficient chemical
fixation of CO2 to prepare various 2-oxazolidinone and
a-hydroxyl ketone scaffolds in excellent yields and selectivity
under mild conditions. This one-pot approach produces valua-
ble carbonyl compounds at high productivity, in which CO2
acts as a dual carbonyl reagent with high atom economy. In
other words, the thermodynamic limitation in the condensa-
tion reaction of 2-aminoalcohols and CO2 is circumvented by
employing this thermodynamically feasible three-component
approach through avoidance of the dehydration step. NMR in-
vestigations and DFT calculations of the reaction mechanism
revealed that such a three-component reaction proceeds
through the successive formation of a-alkylidene cyclic carbon-
ate and b-oxopropylcarbamate. Further studies on potential
applications and mechanistic understanding are underway.
[1] Selected reviews: a) M. Peters, B. Kohler, W. Kuckshinrichs, W. Leitner, P.
Markewitz, T. E. Mꢁller, ChemSusChem 2011, 4, 1216–1240; b) M. He, Y.
Sun, B. Han, Angew. Chem. Int. Ed. 2013, 52, 9620–9633; Angew. Chem.
2013, 125, 9798–9812; c) M. Aresta, A. Dibenedetto, A. Angelini, Chem.
Rev. 2014, 114, 1709–1742; d) C. Maeda, Y. Miyazaki, T. Ema, Catal. Sci.
Technol. 2014, 4, 1482–1497; e) B. Yu, L. N. He, ChemSusChem 2015, 8,
52–62.
[2] Reviews: a) X. B. Lu, D. J. Darensbourg, Chem. Soc. Rev. 2012, 41, 1462–
1484; b) Z. Z. Yang, L. N. He, J. Gao, A. H. Liu, B. Yu, Energy Environ. Sci.
2012, 5, 6602–6639; c) N. Kielland, C. J. Whiteoak, A. W. Kleij, Adv.
Synth. Catal. 2013, 355, 2115–2138; d) Q. Liu, L. Wu, R. Jackstell, M.
Beller, Nat. Commun. 2015, 6, 5933.
[3] a) R. Roers, G. L. Verdine, Tetrahedron Lett. 2001, 42, 3563–3565; b) M. L.
Leroux, T. Le Gall, C. Mioskowski, Tetrahedron: Asymmetry 2001, 12,
1817–1823.
[4] a) D. A. Evans, M. D. Ennis, T. Le, N. Mandel, G. Mandel, J. Am. Chem. Soc.
1984, 106, 1154–1156; b) D. A. Evans, K. T. Chapman, J. Bisaha, J. Am.
Chem. Soc. 1988, 110, 1238–1256.
[5] J. V. N. Vara Prasad, Curr. Opin. Microbiol. 2007, 10, 454–460.
[6] For selected reports on the synthesis of oxazolidinone derivatives from
propargylic amines and CO2, see: a) M. Feroci, M. Orsini, G. Sotgiu, L.
Rossi, A. Inesi, J. Org. Chem. 2005, 70, 7795–7798; b) S. Yoshida, K.
Fukui, S. Kikuchi, T. Yamada, Chem. Lett. 2009, 38, 786–787; c) M. Yoshi-
da, T. Mizuguchi, K. Shishido, Chem. Eur. J. 2012, 18, 15578–15581; d) S.
Hase, Y. Kayaki, T. Ikariya, Organometallics 2013, 32, 5285–5288; e) J.
&
ChemSusChem 2016, 9, 1 – 6
www.chemsuschem.org
4
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Communications
Hu, J. Ma, Q. Zhu, Z. Zhang, C. Wu, B. X. Han, Angew. Chem. Int. Ed.
2015, 54, 5399–5403; Angew. Chem. 2015, 127, 5489–5493.
[10] For selected examples of the synthesis of b-oxopropylcarbamates, see:
a) H.-S. Kim, J.-W. Kim, S.-C. Kwon, S.-C. Shim, T.-J. Kim, J. Organomet.
Chem. 1997, 545–546, 337–344; b) Q. Zhang, F. Shi, Y. Gu, J. Yang, Y.
Deng, Tetrahedron Lett. 2005, 46, 5907–5911; c) C.-R. Qi, H.-F. Jiang,
Green Chem. 2007, 9, 1284–1286; d) Q. W. Song, W. Q. Chen, R. Ma, A.
Yu, Q. Y. Li, Y. Chang, L. N. He, ChemSusChem 2015, 8, 821–827.
[11] For a-hydroxyl ketones synthesis from hydration reaction of propargylic
alcohols, see: a) H. He, C. Qi, X. Hu, Y. Guan, H. Jiang, Green Chem. 2014,
16, 3729–3733; b) Y. Zhao, Z. Yang, B. Yu, H. Zhang, H. Xu, L. Hao, B.
Han, Z. Liu, Chem. Sci. 2015, 6, 2297–2301. For other methods for a-hy-
droxyl ketones synthesis, see Figure S4 in the Supporting Information.
[12] For examples of silver-promoted activation of alkynes, see: a) X.-Q. Yao,
C.-J. Li, Org. Lett. 2005, 7, 4395–4398; b) J. Liu, Z. Fang, Q. Zhang, Q.
Liu, X. Bi, Angew. Chem. Int. Ed. 2013, 52, 6953–6957; Angew. Chem.
2013, 125, 7091–7095; c) F. Li, J. Nie, L. Sun, Y. Zheng, J.-A. Ma, Angew.
Chem. Int. Ed. 2013, 52, 6255–6258; Angew. Chem. 2013, 125, 6375–
6378; d) C. He, S. Guo, J. Ke, J. Hao, H. Xu, H. Chen, A. Lei, J. Am. Chem.
Soc. 2012, 134, 5766–5769.
[7] For recent examples of the synthesis of 2-oxazolidinone derivatives,
see: a) Y. L. Gu, Q. H. Zhang, Z. Y. Duan, J. Zhang, S. G. Zhang, Y. Q.
Deng, J. Org. Chem. 2005, 70, 7376–7380; b) H.-F. Jiang, J.-W. Zhao, Tet-
rahedron Lett. 2009, 50, 60–62; c) Q. W. Song, B. Yu, X. D. Li, R. Ma, Z. F.
Diao, R. G. Li, W. Li, L. N. He, Green Chem. 2014, 16, 1633–1638.
[8] For typical reports on reactions of 2-aminoethanols and CO2, see: a) K.-i.
Tominaga, Y. Sasaki, Synlett 2002, 0307–0309; b) C. J. Dinsmore, S. P.
Mercer, Org. Lett. 2004, 6, 2885–2888; c) S.-i. Fujita, H. Kanamaru, H.
Senboku, M. Arai, Int. J. Mol. Sci. 2006, 7, 438–450; d) J. Paz, C. Pꢂrez-
Balado, B. Iglesias, L. MuÇoz, Synlett 2009, 395–398; e) J. Paz, C. Pꢂrez-
Balado, B. Iglesias, L. MuÇoz, J. Org. Chem. 2010, 75, 3037–3046; f) R.
Juꢃrez, P. Concepcion, A. Corma, H. Garcia, Chem. Commun. 2010, 46,
4181–4183; g) S. Pulla, C. M. Felton, Y. Gartia, P. Ramidi, A. Ghosh, ACS
Sustainable Chem. Eng. 2013, 1, 309–312; h) M. Tamura, M. Honda, K.
Noro, Y. Nakagawa, K. Tomishige, J. Catal. 2013, 305, 191–203; i) Y.
Takada, S. W. Foo, Y. Yamazaki, S. Saito, RSC Adv. 2014, 4, 50851–50857;
j) J. R. Khusnutdinova, J. A. Garg, D. Milstein, ACS Catal. 2015, 5, 2416–
2422.
[13] G. A. Bowmaker, Effendy, J. V. Hanna, P. C. Healy, S. P. King, C. Pettinari,
B. W. Skelton, A. H. White, Dalton Trans. 2011, 40, 7210–7218.
[9] a) H. Zhou, Y. M. Wang, W. Z. Zhang, J. P. Qu, X. B. Lu, Green Chem. 2011,
13, 644–650; b) D. Adhikari, A. W. Miller, M.-H. Baik, S. T. Nguyen, Chem.
Sci. 2015, 6, 1293–1300; c) B.-S. Wang, E. H. M. Elageed, D.-W. Zhang,
S.-J. Yang, S. Wu, G.-R. Zhang, G.-H. Gao, ChemCatChem 2014, 6, 278–
283.
Received: April 11, 2016
Revised: May 12, 2016
Published online on && &&, 0000
ChemSusChem 2016, 9, 1 – 6
www.chemsuschem.org
5
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

COMMUNICATIONS
Q.-W. Song, Z.-H. Zhou, M.-Y. Wang,
K. Zhang, P. Liu, J.-Y. Xun, L.-N. He*
&& – &&
Thermodynamically Favorable
Synthesis of 2-Oxazolidinones through
Silver-Catalyzed Reaction of
Propargylic Alcohols, CO2, and 2-
Aminoethanols
Three in a pot: A thermodynamically
feasible pathway for CO2 conversion is
successfully performed to concurrently
synthesize 2-oxazolidinones and
hols, CO2, and 2-aminoalcohols. As
a consequence, the thermodynamic lim-
itation for the condensation reaction of
2-aminoalcohols and CO2 is circumvent-
ed by avoiding the dehydration step.
a-hydroxyl ketones through a three-
component reaction of propargylic alco-
&
ChemSusChem 2016, 9, 1 – 6
www.chemsuschem.org
6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!