2
Table 2. Scope of Substratesa
Entry
1
Product 2
Isolated Yield (%)
93
2
b
2
85
72
78
2
c
b
3
2
d
4
2
e
Scheme 1. A possible reaction mechanism
This work was supported by a Grant-in-Aid for Young
Scientists (A) (No. 25708017) from JSPS, Japan.
b
5
65
2
f
Supporting
Information
is
available
on
6
7
86
70
http://dx.doi.org/10.1246/cl.******.
2
g
References and Notes
†
Present address: Department of Chemistry, Graduate School of
Science, Kyoto University, Kyoto 606-8502
Present address: Department of Basic Science, Graduate School
2
h
‡
of Art and Sciences, The University of Tokyo, Tokyo 153-8902.
a) New and Future Developments in Catalysis, Activation of
Carbon Dioxide, ed. By S. L. Suib, Elsevier: Amsterdam, 2013. b)
Angelini, Chem. Rev. 2014, 114, 1709–1742.
1
2
8
68
65
2
i
b
9
a) K. Nogi, T. Fujihara, J. Terao, Y. Tsuji, J. Am. Chem. Soc.
2
016, 138, 5547–5550. b) Y. Tani, T. Fujihara, J. Terao, Y. Tsuji,
2
j
J. Am. Chem. Soc. 2014, 136, 17706–17709. c) T. Fujihara, Y.
Tani, K. Semba, J. Terao, Y. Tsuji, Angew. Chem. Int. Ed. 2012,
51, 11487–11490. d) T. Fujihara, K. Nogi, T. Xu, J. Terao, Y.
Tsuji, J. Am. Chem. Soc. 2012, 134, 9106–9109.
c
1
0
1
64
53
3
4
a) C. Martin, G. Fiorani, A. W. Kleij, ACS Catal. 2015, 5, 1353–
1
2
k
370. b) C. Maeda, Y. Miyazaki, T. Ema, Catal. Sci. Technol.
014, 4, 1482–1497. c) M. R. Kember, A. Buchard, C. K.
2
d
1
Williams, Chem. Commun, 2011, 47, 141–163. d) A. Decortes, A.
M. Castilla, A. W. Kleij, Angew. Chem. Int. Ed. 2010, 49, 9822–
2
l
9
837. e) B. Schäffner, F. Schäffner, S. P. Verevkin, A. Börner,
a
Reaction conditions: epoxide (1, 2.0 mmol), MgCl
2
(0.10 mmol, 5.0
(1 atm).
Reaction was carried out with 0.50 mmol scale. Substrate 0.50 mmol
Chem. Rev. 2010, 110, 4554–4581.
mol %), in DMF (2.0 mL), at 100 °C, for 18 h, under CO
2
a) C.-Y. Yu, H.-J. Chuang, B.-T. Ko, Catal. Sci. Technol, 2016, 6,
1779–1791. b) S. Narang, R. Mehta, S. N. Upadhyay, Curr. Org.
Chem. Soc. Rev. 2012, 41, 1462–1484. d) M. R. Kember, A.
Buchard, C. K. Williams, Chem. Commun. 2011, 47, 141–163. e)
S. Klaus, M. W. Lehenmeier, C. E. Anderson, B. Rieger, Coord.
Chem. Rev. 2011, 255, 1460–1479.
b
c
d
scale, MgCl
2
(0.050 mmol, 10 mol%), at 40 °C, for 5 h. 1l (0.50 mmol),
MgCl (0.050 mmol, 10 mol%), in DMF (0.50 mL) at 100 °C, 72 h.
2
A possible catalytic cycle is shown in Scheme 1. First,
epoxide 1 is activated by the coordination of MgCl to form
A (step 1). Then, the chloro anion attacks a sterically less
hindered site of A, generating B (step 2). The reaction of
CO
carbonate 2 via D and MgCl
In conclusion, we found that MgCl
cheap and easy-to-handle reagent, catalyzed the reaction of
epoxides with CO . The reaction afforded various cyclic
carbonates in good to high yields under an atmospheric
pressure of CO
2
5
6
a) N. Kihara, N. Hara, T. Endo, J. Org. Chem. 1993, 58, 6198–
6202. b) T. Iwasaki, N. Kihara, T. Endo, Bull. Chem. Soc. Jpn.
2
000, 73, 713–719.
a) T. Ema, Y. Miyazaki, J. Shimonishi, C. Maeda, J.-y. Hasegawa,
J. Am. Chem, Soc. 2014, 136, 15270–15279. b) C. Maeda, T.
Taniguchi, K. Ogawa, T. Ema, Angew. Chem. Int. Ed. 2015, 54,
2
with B provides C (step 3). Finally, C affords cyclic
is regenerated (steps 4 and 5).
, a stable, abundant,
2
1
34–138.
2
7
a) J. Rintjema, R. Epping, G. Fiorani, E. Martin, E. C. Escudero-
J. A. Kozak, J. Wu, X. Su, F. Simeon, A. Hatton, T. F. Jamison, J.
Am. Chem. Soc. 2013, 135, 18497–18501.
2
8
9
2
.
Y. Ren, J.-J. Shim, ChemCatChem 2013, 5, 1344–1349.