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Bio-inspired Water-Driven Catalytic Enantioselective Protonation
Si Joon Park1, In-Soo Hwang1, Young Jun Chang1
1Department of Chemistry, Sungkyunkwan University, Suwon, 16419, Korea.
Journal of the American Chemical Society
|January 13, 2021
Summary
Synthetic chemists can now achieve enantioselective protonation in water using a glyoxalase I mimic. This breakthrough overcomes challenges posed by rapid proton transfer, enabling controlled synthesis.
Area of Science:
- Organic Chemistry
- Biomimetic Catalysis
Background:
- Enantioselective protonation of prochiral carbanions is vital in biological systems.
- Achieving this synthetically in water is challenging due to rapid, uncontrolled proton transfer, leading to racemic products.
Purpose of the Study:
- To develop a synthetic method for highly enantioselective protonation in water.
- To mimic the catalytic action of enzymes like glyoxalase I.
Main Methods:
- Utilized an on-water catalytic system employing a glyoxalase I mimic.
- Investigated the role of water's hydrogen bonding and employed biphasic microfluidic conditions.
Main Results:
- Demonstrated highly enantioselective catalytic isomerization of hemithioacetals via protonation of an ene-diol intermediate.
- Showcased that on-water conditions activate the reaction and prevent racemic protonation by controlling water access to the transition state.
Conclusions:
- Water plays a crucial role in enabling enantioselective protonation under specific catalytic conditions.
- The developed method successfully mimics enzymatic activity for challenging protonation reactions.
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