Journal of the American Chemical Society
Communication
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distance of adjacent surfaces in a channel is 6.277(3) Å. This
close proximity and appropriate spatial orientation of Co(salen)
units thus offer the possibility that H2O activated by one
Co(salen) could attack the epoxide activated by another
Co(salen) (Figure S11), affording the product with impressive
activity even at a low C/S ratio. Generation of cooperative
activation in a solid catalyst is important since lots of catalytic
transformations proceed through a dual activation pathway, but
it remains a challenge because of its inability to elaborately
control the proper proximity and the conformation of active
centers.20 This work highlights the potential of making
heterogeneous dual-active catalysts by using MOFs as support
structures.
In summary, we have constructed two chiral, robust, porous
MOFs based on dicarboxylate-functionalized Ni(salen) and
Co(salen)(OAc) ligands. The Co(salen) units accessible via the
open MOF channels were utilized to generate an efficient
heterogeneous asymmetric catalyst for HKR of epoxides to
afford the product at up to 99.5% ee. The MOF catalyst
features a high local density of coorperative bis[Co(salen)]
motifs, exhibiting improved catalytic performance relative to
the monomeric catalysts at low C/S ratios. The solid catalyst
can be easily recycled and reused without any apparent loss of
catalytic activity and enantioselectivity. The ready tunability of
such a modular approach based on metallosalens promises to
lead to a number of chiral solid catalysts with unique and
practically useful enantioselective functions.
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J. T.; Nguyen, S. T. J. Am. Chem. Soc. 2011, 133, 13251. (e) Ma, L.;
Falkowski, J. M.; Abney, C.; Lin, W. Nat. Chem. 2010, 2, 838.
(f) Tanaka, K.; Odaa, S.; Shirob, M. Chem. Commun. 2008, 820.
(g) Tanaka, K.; Otani, K.-i. New J. Chem. 2010, 34, 2389. (h) Ingleson,
M. J.; Barrio, J. P.; Bacsa, J.; Dickinson, C.; Park, H.; Rosseinsky, M. J.
Chem. Commun. 2008, 11, 1287. (i) Banerjee, M.; Das, S.; Yoon, M.;
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ASSOCIATED CONTENT
■
(11) (a) Yuan, G.; Zhu, C.; Xuan, W.; Cui, Y. Chem.Eur. J. 2009,
15, 6428. (b) Xiang, S.; Zhang, Z.; Zhao, C.; Hong, K.; Zhao, X.; Ding,
D.; Xie, M.; Wu, C.; Das, M. C.; Gill, R.; Thomas, K. M.; Chen, B. Nat.
Commun. 2011, 2, 204. (c) Jeon, Y. M.; Heo, J.; Mirkin, C. A. J. Am.
Chem. Soc. 2007, 129, 7480. (d) Yuan, G.; Zhu, C.; Liu, Y.; Cui, Y.
Chem. Commun. 2010, 47, 3180.
(12) (a) Schaus, S. E.; Brandes, B. D.; Larrow, J. F.; Tokunaga, M.;
Hansen, K. B.; Gould, A. E.; Furrow, M. E.; Jacobsen, E. N. J. Am.
Chem. Soc. 2002, 124, 1307. (b) Nielsen, L. P. C.; Stevenson, C. P.;
Blackmond, D. G.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 1360.
(13) (a) Breinbauer, R.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2000,
39, 3604. (b) Annis, D. A.; Jacobsen, E. N. J. Am. Chem. Soc. 1999,
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(d) Ready, M. J.; Jacobsen, E. N. J. Am. Chem. Soc. 2001, 123, 2687.
(14) (a) Yang, H.; Zhang, L.; Zhong, L.; Yang, Q.; Li, C. Angew.
Chem., Int. Ed. 2007, 46, 6861. (b) Ma, J.; Cahard, D. Angew. Chem.,
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S
* Supporting Information
Experimental procedures and characterization data. This
material is available free of charge via the Internet at http://
AUTHOR INFORMATION
■
Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by NSFC-21025103 and 20971085,
“973” Programs (2009CB930403), and Shanghai Science and
Technology Committee (10DJ1400100).
(15) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7.
(16) Oh, C. R.; Choo, D. J.; Shim, W. H.; Lee, D. H.; Roh, E. J.; Lee,
S.; Song, C. E. Chem. Commun. 2003, 1100.
(17) Thakur, S. S.; Li, W.; Shin, C.; Kim, G. Catal. Lett. 2005, 104,
151.
(18) We also performed HKR reactions using (R)- and (S)-phenyl
glycidyl ether as substrate, and their conversions were found to be 53
and 15%, respectively, in 36 h. This means the (R) enantiomer reacts
with H2O about 3.5 times faster than the (S) enantiomer in the
presence of (R)-2.
(19) Because most MOFs, including 2, are mechanically unstable,
they tend to fracture into smaller particles by magnetic stirring (Figure
S19). It is thus hard to obtain quantitative kinetic parameters since the
reaction rate depends on the catalyst sizes and the stirring rate.
(20) (a) Thomas, J. M.; Raja, R. Acc. Chem. Res. 2008, 41, 708.
(b) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187.
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