Bio-inspired Water-Driven Catalytic Enantioselective Protonation
| Autor: | Insoo Hwang, Choong Eui Song, Young Jun Chang, Si Joon Park |
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| Rok vydání: | 2021 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 143:2552-2557 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.0c11815 |
| Popis: | Catalytic enantioselective protonation of a prochiral carbanion in water is a common transformation in biological systems, but has been beyond the capability of synthetic chemists since unusually rapid movement of a proton in water leads to uncontrolled racemic protonation. Herein we show a crucial role of water, which enables a highly enantioselective glyoxalase I-mimic catalytic isomerization of hemithioacetals which proceeds via enantioselective protonation of an ene-diol intermediate. The use of on-water condition turns on this otherwise extremely unreactive catalytic reaction as a result of the strengthened hydrogen bonds of water molecules near the hydrophobic reaction mixture. Furthermore, under on-water conditions, especially under biphasic microfluidic on-water conditions, access of bulk water into the enantio-determining transition state is efficiently blocked, consequently enabling the enantioselective introduction of a highly ungovernable proton to a transient enediol intermediate, which mimics the action of enzymes. |
| Databáze: | OpenAIRE |
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