AI Article Synopsis
- A new method has been developed for an enantiodivergent epoxide opening reaction, allowing the selective production of both chiral alcohol forms using different titanium complexes.
- Kinetic studies suggest that the way these complexes differentiate between enantiomers depends on their structure: mononuclear complexes rely on enthalpy, while dinuclear complexes depend on entropy.
- Theoretical calculations provide insights into how mononuclear catalysts control enantiomer formation and identify the active catalyst in dinuclear systems, offering a potential approach for developing more flexible asymmetric catalysis using distinct metal complexes.
Article 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)Ti 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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| http://dx.doi.org/10.1002/anie.202309525 | DOI Listing |
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A Nuclearity-Dependent Enantiodivergent Epoxide Opening via Enthalpy-Controlled Mononuclear and Entropy-Controlled Dinuclear (Salen)Titanium Catalysis.
Angew Chem Int Ed Engl
September 2023
Department of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China.
Article Synopsis
- A new method has been developed for an enantiodivergent epoxide opening reaction, allowing the selective production of both chiral alcohol forms using different titanium complexes.
- Kinetic studies suggest that the way these complexes differentiate between enantiomers depends on their structure: mononuclear complexes rely on enthalpy, while dinuclear complexes depend on entropy.
- Theoretical calculations provide insights into how mononuclear catalysts control enantiomer formation and identify the active catalyst in dinuclear systems, offering a potential approach for developing more flexible asymmetric catalysis using distinct metal complexes.
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