Publication Details |
| Category | Text Publication |
| Reference Category | Journals |
| DOI | 10.1021/ja103448u |
| Title (Primary) | Reversible biological Birch reduction at an extremely low redox potential |
| Author | Kung, J.W.; Baumann, S.; von Bergen, M.; Müller, M.; Hagedoorn, P.-L.; Hagen, W.R.; Boll, M. |
| Source Titel | Journal of the American Chemical Society |
| Year | 2010 |
| Department | PROTEOM |
| Volume | 132 |
| Issue | 28 |
| Page From | 9850 |
| Page To | 9856 |
| Language | englisch |
| Abstract | The Birch reduction of aromatic rings to cyclohexadiene compounds is widely used in chemical synthesis and requires solvated electrons, the most potent reductants known in organic chemistry. Benzoyl-coenzyme A (CoA) reductases (BCR) are key enzymes in the anaerobic bacterial degradation of aromatic compounds and catalyze an analogous reaction under physiological conditions. Class I BCRs are FeS enzymes and couple the reductive dearomatization of benzoyl-CoA to cyclohexa-1,5-diene-1-carboxyl-CoA (dienoyl-CoA) to a stoichiometric ATP hydrolysis. Here, we report on a tungsten-containing class II BCR from Geobacter metallireducens that catalyzed the fully reversible, ATP-independent dearomatization of benzoyl-CoA to dienoyl-CoA. BCR additionally catalyzed the disproportionation of dienoyl-CoA to benzoyl-CoA/monoenoyl-CoA and the four- and six-electron reduction of benzoyl-CoA in the presence of a reduced low-potential bridged 2,2'-bipyridyl redox dye. Reversible redox titration experiments in the presence of this redox dye revealed a midpoint potential of E0'= -622 mV for the benzoyl-CoA/dienoyl-CoA couple, which is far below the values of other known reversible substrate/product redox couples in enzymology. This work demonstrates the efficiency of reversible metalloenzyme catalysis, which in chemical synthesis can only be achieved under essentially irreversible conditions. |
| Persistent UFZ Identifier | https://www.ufz.de/index.php?en=20939&ufzPublicationIdentifier=10219 |
| Kung, J.W., Baumann, S., von Bergen, M., Müller, M., Hagedoorn, P.-L., Hagen, W.R., Boll, M. (2010): Reversible biological Birch reduction at an extremely low redox potential J. Am. Chem. Soc. 132 (28), 9850 - 9856 10.1021/ja103448u |
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