ja7b07921_si_002.cif (7.73 MB)
Modulating the Performance of an Asymmetric Organocatalyst by Tuning Its Spatial Environment in a Metal–Organic Framework
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posted on 2017-09-20, 14:18 authored by Lujia Liu, Tian-You Zhou, Shane G. TelferSystematically 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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reaction productapproach benefitsreaction ratepore structureAsymmetric OrganocatalystMUF -77 frameworksite environmentsaldol reactionsmodulator groupspore architecturesingle-site catalystsaldol productsstereochemical preferenceproline catalystSystematic engineeringProlinyl groupsprolinyl groupresults offerSpatial Environmentframework linkers
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