Modulating the Performance of an Asymmetric Organocatalyst by Tuning Its Spatial Environment in a Metal–Organic Framework

Systematically tuning the spatial environment around the active sites of synthetic catalysts is a difficult challenge. Here, we show how this can be accomplished in the pores of multicomponent metal–organic frameworks. This relies on embedding a catalytic unit in a pore of the MUF-77 framework and t...

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Published inJournal of the American Chemical Society Vol. 139; no. 39; pp. 13936 - 13943
Main Authors Liu, Lujia, Zhou, Tian-You, Telfer, Shane G
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 04.10.2017
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
ENZYME MIMICS
STABILITY
FUNCTIONAL-GROUPS
PORE ENVIRONMENT
NONCOVALENT INTERACTIONS
MOFS
ADSORPTION
ENANTIOSELECTIVITY REVERSAL
TRANSFORMATIONS
HETEROGENEOUS CATALYSTS
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Summary:Systematically tuning the spatial environment around the active sites of synthetic catalysts is a difficult challenge. Here, we show how this can be accomplished in the pores of multicomponent metal–organic frameworks. This relies on embedding a catalytic unit in a pore of the MUF-77 framework and then tuning its environment by introducing different functional groups to the surrounding linkers. This approach benefits from the structural regularity of MUF-77, which places each component in a precise location to circumvent disorder. Prolinyl groups, which are catalytically competent toward asymmetric aldol reactions, were selected as the catalytic unit. Since every prolinyl group is positioned in an identical environment, correlations between the pore architecture and the activity of these single-site catalysts can be elucidated. Systematic engineering of the pore structure, which is achieved by installing modulator groups on the framework linkers, impacts on the reaction rate and the enantiomeric excess of the aldol products. Furthermore, the spatial environment around the proline catalyst can override its innate stereochemical preference to dictate the preferred enantiomer of the reaction product. These results offer a new way to design three-dimensional active site environments for synthetic catalysts.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b07921