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Updated: Jul 21, 2025

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
A Nuclearity-Dependent Enantiodivergent Epoxide Opening via Enthalpy-Controlled Mononuclear and Entropy-Controlled
Shengxiao Li1, Hui Zhu2, Longfei Li1
1Department of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China.
Abstract:
A nuclearity-dependent enantiodivergent epoxide opening reaction has been developed, in which both antipodes of chiral alcohol products are selectively accessed by mononuclear (salen)TiIII complex and its self-assembled oxygen-bridged dinuclear counterparts within the same stereogenic ligand scaffold. Kinetic studies based on the Eyring equation revealed an enthalpy-controlled enantio-differentiation mode in mononuclear catalysis, whereas an entropy-controlled one in dinuclear catalysis. DFT calculations outline the origin of the enantiocontrol of the mononuclear catalysis and indicate the actual catalyst species in the dinuclear catalytic system. The mechanistic insights may shed a light on a strategy for stereoswichable asymmetric catalysis utilizing nuclearity-distinct transition-metal complexes.
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