Aberasturia, C. A. Ramírez-Lópeza, J. Nieto-Mestrea, B. Maestro-Madur-
gaa and M. Belsuéa, Chem. Eng. J., 2011, 175, 505.
hydroxyl groups and alkali metal cation that actually accelerates
the cycloaddition. The halide anion plays a special role in this
process. First, the nucleophilic attack of halide anion signifi-
cantly accelerates the epoxy ring opening. Second, it is the
leaving group in the intramolecular cyclic step. So the catalytic
activity of the alkali halides should increase with increasing
nucleophilicity and leaving ability of the halide anions. The
iodide ion is a good nucleophile as well as a good leaving
group,37 therefore shows highest catalytic activity.
One point that should be noted is that small anions are sol-
vated more strongly than large anions in a protic solvent because
the solvent approaches a small anion more closely and forms
stronger hydrogen bonds. Therefore, when an anion acts as a
nucleophile, more energy is required to remove the solvent from
a small, strongly solvated ion such as chlorine than from a large
and less strongly solvated ion like iodide. The requirement of
more energy to strip off their solvent molecules of smaller
anions reduces their nucleophilicity.37 Glycerol and PG as hydro-
xylic solvents are rich in the coupled reaction system studied in
this work. Therefore, the solvent effects of glycerol and PG
weaken the nucleophilic attack of Cl− and Br−, and have less
effect on that of I−. Then, the solvent effects as another factor
also contribute to the relative catalytic activities of the alkali
halides, I− > Br− > Cl−, as shown in Table 1.
3 (a) D. J. Darensbourg, Chem. Rev., 2007, 107, 2388; (b) C. T. Cohen,
T. Chu and G. W. Coates, J. Am. Chem. Soc., 2005, 127, 10869.
4 (a) F. Shi, Y. Q. Deng, T. L. SiMa, J. J. Peng, Y. L. Gu and B. T. Qiao,
Angew. Chem., Int. Ed., 2003, 42, 3257; (b) A. Ion, V. Parvulescu,
P. Jacobs and D. D. Vos, Green Chem., 2007, 9, 158.
5 (a) R. N. Salvatore, S. I. Shin, A. S. Nagle and K. W. Jung, J. Org.
Chem., 2001, 66, 1035; (b) C. Wu, H. Cheng, R. Liu, Q. Wang, Y. Hao,
Y. Yu and F. Zhao, Green Chem., 2010, 12, 1811.
6 (a) Z. F. Zhang, Y. Xie, W. J. Li, S. Q. Hu, J. L. Song, T. Jiang and B.
X. Han, Angew. Chem., Int. Ed., 2008, 47, 1127; (b) A. D. Getty, C. Tai,
J. C. Linehan, P. G. Jessop, M. M. Olmstead and A. L. Rheingold, Orga-
nometallics, 2009, 28, 5466.
7 J. B. Johnson and T. Rovis, Acc. Chem. Res., 2008, 41, 327.
8 (a) C. H. Zhou, J. N. Beltramini, Y. X. Fana and G. Q. Lu, Chem. Soc.
Rev., 2008, 37, 527; (b) Y. G. Zheng, X. L. Chen and Y. C. Shen, Chem.
Rev., 2008, 108, 5253; (c) A. Behr, J. Eilting, K. Irawadi, J. Leschinski
and F. Lindner, Green Chem., 2008, 10, 13.
9 (a) Y. Shen, S. Zhang, H. Li, Y. Ren and H. Liu, Chem.–Eur. J., 2010,
16, 7368; (b) S. Demirel, K. Lehnert, M. Lucas and P. Claus, Appl.
Catal., B, 2007, 70, 637.
10 (a) T. Jiang, Y. X. Zhou, S. G. Liang, H. Z. Liu and B. X. Han, Green
Chem., 2009, 11, 1000; (b) M. A. Dasari, P. P. Kiatsimkul, W. R. Sutterlin
and G. J. Suppes, Appl. Catal., A, 2005, 281, 225.
11 B. Katryniok, S. Paul, V. Bellière-Baca, P. Reye and F. Dumeignil, Green
Chem., 2010, 12, 2079.
12 (a) G. Rokicki, P. Rakoczy, P. Parzuchowski and M. Sobiecki, Green
Chem., 2005, 7, 529; (b) M. J. Climent, A. Corma, P. D. Frutos,
S. Iborra, M. Noy, A. Velty and P. Concepción, J. Catal., 2010, 269, 140;
(c) S. C. Kim, Y. H. Kim, H. Lee, D. Y. Yoon and B. K. Song, J. Mol.
Catal. B: Enzym., 2007, 49, 75; (d) K. T. Tan, K. T. Lee and A.
R. Mohamed, Fuel, 2010, 89, 3833; (e) J. R. Ochoa-Gómez, O. Gómez-
Jiménez-Aberasturi, B. Maestro-Madurga, A. Pesquera-Rodríguez,
C. Ramírez-López, L. Lorenzo-Ibarreta, J. Torrecilla-Soria and M.
C. Villarán-Velasco, Appl. Catal., A, 2009, 366, 315; (f) M. Aresta,
A. Dibenedetto, F. Nocito and C. Ferragina, J. Catal., 2009, 268, 106;
(g) M. G. Alvarez, A. M. Segarra, S. Contreras, J. E. Sueiras, F. Medina
and F. Figueras, Biochem. Eng. J., 2010, 161, 340.
13 (a) J. Hu, J. Li, Y. Gu, Z. Guan, W. Mo, Y. Ni, T. Li and G. Li, Appl.
Catal., A, 2010, 386, 188; (b) T. Mizuno, T. Nakai and M. Mihara, Het-
eroat. Chem., 2010, 21, 99; (c) M. Aresta, A. Dibenedetto, F. Nocito and
C. Pastore, J. Mol. Catal. A: Chem., 2006, 257, 149; (d) A. Dibenedetto,
A. Angelini, M. Aresta, J. Ethiraj, C. Fragale and F. Nocito, Tetrahedron,
2011, 67, 1308; (e) J. Georgea, Y. Patel, S. M. Pillai and P. Munshic, J.
Mol. Catal. A: Chem., 2009, 304, 1.
14 (a) C. García-Sancho, R. Moreno-Tost, J. M. Mérida-Robles,
J. Santamaría-González, A. Jiménez-López and P. M. Torres, Catal.
Today, 2011, 167, 84; (b) J. M. Clacens, Y. Pouilloux and J. Barrault,
Appl. Catal., A, 2002, 227, 181.
15 (a) J. W. Huang and M. Shi, J. Org. Chem., 2003, 68, 6705; (b) J. Song,
Z. Zhang, S. Hu, T. Wu, T. Jiang and B. Han, Green Chem., 2009, 11,
1031.
16 (a) K. Yamaguchi, K. Ebitani, T. Yoshida, H. Yoshida and K. Kaneda, J.
Am. Chem. Soc., 1999, 121, 4526; (b) T. Yano, H. Matsui, T. Koike,
H. Ishiguro, H. Fujihara, M. Yoshihara and T. Maeshima, Chem.
Commun., 1997, 1129.
17 (a) J. Meléndez, M. North and R. Pasquale, Eur. J. Inorg. Chem., 2007,
3323; (b) F. Li, C. Xia, L. Xu, W. Sun and G. Chen, Chem. Commun.,
2003, 2042; (c) P. Yan and H. Jing, Adv. Synth. Catal., 2009, 351, 1325;
(d) M. Ulusoy, E. Cetinkaya and B. Cetinkaya, Appl. Organomet. Chem.,
2009, 23, 68.
Conclusions
The one-pot reaction of CO2, glycerol and PO to produce GC,
PC and PG has been studied using various alkali metal halides
as the catalysts. Using PO as coupling agent, glycerol and CO2
can be effectively converted into value-added products GC, PC
and PG. Glycerol and PG, which are the reactant and product,
respectively, act as the co-catalysts to promote the key step of the
coupled route significantly. The catalytic activities of the corre-
sponding alkali halides follow the order of I− > Br− > Cl−, deter-
mined by their relative nucleophilicity and basicity. Among the
investigated alkali halides, KI has the highest activity. At optimal
reaction conditions, the highest conversion of glycerol can reach
90%. We believe that the idea to convert glycerol and CO2
simultaneously by adding coupling agents to circumvent the
thermodynamic limitation may be used to develop other routes
for effective transformation of glycerol and CO2.
Acknowledgements
The authors thank the National Natural Science Foundation of
China (21173239, 20932002, 21021003), Ministry of Science
and Technology of China (2011CB808603), and Chinese
Academy of Sciences (KJCX2.YW.H30).
18 (a) K. Nakano, S. Hashimoto and K. Nozaki, Chem. Sci., 2010, 1, 369;
(b) J. Meléndez, M. North and P. Villuendas, Chem. Commun., 2009,
2577.
19 Y. Du, F. Cai, D. L. Kong and L. N. He, Green Chem., 2005, 7, 518.
20 Y. Xie, Z. Zhang, T. Jiang, J. He, B. Han, T. Wu and K. Ding, Angew.
Chem., Int. Ed., 2007, 46, 7255.
21 (a) W. N. Sit, S. M. Ng, K. Y. Kwong and C. P. Lau, J. Org. Chem.,
2005, 70, 8583; (b) K. Motokura, S. Itagaki, Y. Iwasawa, A. Miyaji and
T. Baba, Green Chem., 2009, 11, 1876; (c) T. Takahashi, T. Watahiki,
S. Kitazume, H. Yasuda and T. Sakakura, Chem. Commun., 2006, 1664.
22 (a) X. Zhang, D. Wang, N. Zhao, A. S. N. Al-Arifi, T. Aouak, Z.
A. Al-Othman, W. Wei and Y. Sun, Catal. Commun., 2009, 11, 43;
(b) J. Sun, J. Ren, S. Zhang and W. Cheng, Tetrahedron Lett., 2009, 50, 423;
Notes and references
1 J. S. Tian, C. X. Miao, J. Q. Wang, F. Cai, Y. Du, Y. Zhao and L. N. He,
Green Chem., 2007, 9, 566.
2 (a) Y. H. Chang, T. Jiang, B. X. Han, Z. M. Liu, W. Z. Wu, L. Gao, J.
C. Li, H. X. Gao, G. Y. Zhao and J. Huang, Appl. Catal., A, 2004, 263,
179; (b) S. Y. Huang, S. G. Liu, J. P. Li, N. Zhao, W. Wei and Y. H. Sun,
Catal. Lett., 2006, 112, 187; (c) J. Ma, X. Zhang, N. Zhao, A. S. N. Al-
Arifi, T. Aouak, Z. A. Al-Othman, W. Wei and Y. Sun, J. Mol. Catal. A:
Chem., 2010, 315, 76; (d) J. R. Ochoa-Gómeza, O. Gómez-Jiménez-
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