Enantioselective Enzymatic Naphthoyl Ring Reduction
| Autor: | Julian Haas, Jonathan Fuchs, Matthias Boll, Max Willistein, Sascha Ferlaino, Steffen Lüdeke, Sebastian Estelmann, Michael Müller |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
Birch reduction Tetrahydronaphthalenes 010405 organic chemistry Chemistry Circular Dichroism Organic Chemistry Enantioselective synthesis Absolute configuration Substrate (chemistry) Stereoisomerism General Chemistry Naphthalenes 010402 general chemistry 01 natural sciences Combinatorial chemistry Catalysis 0104 chemical sciences Stereocenter Enzyme catalysis Alicyclic compound Vibrational circular dichroism Coenzyme A Oxidoreductases Oxidation-Reduction |
| Zdroj: | Chemistry - A European Journal. 24:12505-12508 |
| ISSN: | 0947-6539 |
| Popis: | Birch reductions of aromatic hydrocarbons by means of single-electron-transfer steps depend on alkali metals, ammonia, and cryogenic reaction conditions. In contrast, 2-naphthoyl-coenzyme A (2-NCoA) and 5,6-dihydro-2-NCoA (5,6-DHNCoA) reductases catalyze two two-electron reductions of the naphthoyl-ring system to tetrahydronaphthoyl-CoA at ambient temperature. Using a number of substrate analogues, we provide evidence for a Meisenheimer complex-analogous intermediate during 2-NCoA reduction, whereas the subsequent reduction of 5,6-dihydro-2-NCoA is suggested to proceed via an unprecedented cationic transition state. Using vibrational circular dichroism (VCD) spectroscopy, we demonstrate that both enzymatic reductions are highly stereoselective in D2 O, providing an enantioselective pathway to products inaccessible by Birch reduction. Moreover, we demonstrate the power of VCD spectroscopy to determine the absolute configuration of isotopically engendered alicyclic stereocenters. |
| Databáze: | OpenAIRE |
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