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Chemical Science
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thus revealed different reaction pathways between 1- and L1Me4-
catalyzed reactions as a result of the preferential interactions
between substrates and cavity walls in 1. The preferred pathway
involving TS-1 in the homogenous reaction is totally blocked in
the 1-catalyzed reaction; instead, the preferred pathway for the 1-
catalyzed reaction involves TS-3 which has the highest energy
barrier in the homogeneous reactions.
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In summary, a pair of highly porous chiral MOFs were built
from enantiopure BINOL phosphoric acid derived ligands and
10 Cu2(carboxylate)4 SBUs. In the catalytic asymmetric Friedel-
Crafts reactions between indole and imines, CMOF-1 gave the
major product with opposite chirality compared to that obtained
from the corresponding homogeneous catalyst. By structural
analyses and QM/MM calculations, we demonstrated that the flip
15 of handedness originates from the chiral environment of the MOF
cavity, resembling the stereo-control of the enzyme pocket in
enzymatic catalysis. Future efforts will be devoted to designing
CMOFs containing both chiral cavity for enzyme-like stereo-
control and larger open channels for substrate and product
20 transport[24] in order to design highly active and selective MOF
catalysts for organic transformations.
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Dr. M. Zheng, Dr. Y. Liu, C. Wang, Prof. W. Lin
25 Department of Chemistry, CB#3290, University of North Carolina,
Dr. S. Liu
95 [12]Crystallographic data for [R-L1Cu2(H2O)2]·21DMF·12H2O (CMOF-
1): space group C222, a=17.5328(3)Å, b=30.3514(5) Å,
c=49.1818(8) Å, V=26172(1) Å3, Z=2, ρcalcd
=
0.365 g·cm-3,
Research Computing Center
University of North Carolina, Chapel Hill, NC, 27599 (USA)
R1[I>2σ(I)]=0.0650, wR2[I>2σ(I)]=0.180; Crystallographic data for
[R-L2Cu2(H2O)2]·27DMF·17H2O (CMOF-2): space group I4122,
a=24.4616(4)Å, c=71.872(1)Å, V=43006(1)Å3, Z=8, ρcalcd=0.304
≠
30 These authors contributed equally to this work.
† Electronic Supplementary Information (ESI) available: [General
experimental, synthesis and characterization of ligands and CMOFs,
details for single crystal XRD sturcture refinement, PXRD, procedures
and GC traces for asymmetric catalysis, details of QM/MM calculations].
35 See DOI: 10.1039/b000000x/
100
105
g·cm-3,
R1[I>2σ(I)]=0.0271,
wR2[I>2σ(I)]=0.0501.
[R-
L3Cu2(H2O)2]·21DEF·6H2O (CMOF-3): space group P4222, a = b =
18.7440(8) Å, c=29.2590(12) Å, V=10279.8(8) Å3, Z=2, ρcalcd = 0.305
g·cm-3, R1[I>2σ(I)]=0.200, wR2[I>2σ(I)]=0.438; CCDC 852848,
852849 and 859134 contain the supplimentary crystallographic data
for this paper. These data can be obtained free of charge from the
Acknowledgements
Cambridge
[13]TOPOS 4.0,V. A. Blatov, IUCr Comp. Comm. Newsletter 2006, 7, 4.
Crystallographic
Data
Center
via
We thank NSF (CHE-1111490) for financial support and Ms. Kathryn
deKrafft for experimental help. C.W. acknowledge support from the UNC
40 Department of Chemistry for an Ernest L. Eliel fellowship.
110 [14]Topological type: OCETAS (MOF.ttd), determined by TOPOS 4.0.
see ref 7c for more details.
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m2/g. Freeze-drying technique was used in the gas sorption
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