TY - DATA T1 - Modulating the Performance of an Asymmetric Organocatalyst by Tuning Its Spatial Environment in a Metal–Organic Framework PY - 2017/09/20 AU - Lujia Liu AU - Tian-You Zhou AU - Shane G. Telfer UR - https://acs.figshare.com/articles/dataset/Modulating_the_Performance_of_an_Asymmetric_Organocatalyst_by_Tuning_Its_Spatial_Environment_in_a_Metal_Organic_Framework/5422987 DO - 10.1021/jacs.7b07921.s002 L4 - https://ndownloader.figshare.com/files/9355195 KW - reaction product KW - approach benefits KW - reaction rate KW - pore structure KW - Asymmetric Organocatalyst KW - MUF -77 framework KW - site environments KW - aldol reactions KW - modulator groups KW - pore architecture KW - single-site catalysts KW - aldol products KW - stereochemical preference KW - proline catalyst KW - Systematic engineering KW - Prolinyl groups KW - prolinyl group KW - results offer KW - Spatial Environment KW - framework linkers N2 - 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. ER -