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Angew Chem Int Ed Engl. 2014 Sep 8;53(37):9806-11. doi: 10.1002/anie.201404560. Epub 2014 Jul 22.

Unprecedented role of hydronaphthoquinone tautomers in biosynthesis.

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Institut für Pharmazeutische Wissenschaften, Albert-Ludwigs-Universität Freiburg, Albertstrasse 25, 79104 Freiburg (Germany); Present address: Centre of Biomedical Research, Raebareli Road, Lucknow 226 014, Uttar Pradesh (India).


Quinones and hydroquinones are among the most common cellular cofactors, redox mediators, and natural products. Here, we report on the reduction of 2-hydroxynaphthoquinones to the stable 1,4-diketo tautomeric form of hydronaphthoquinones and their further reduction by fungal tetrahydroxynaphthalene reductase. The very high diastereomeric and enantiomeric excess, together with the high yield of cis-3,4-dihydroxy-1-tetralone, exclude an intermediary hydronaphthoquinone. Labeling experiments with NADPH and NADPD corroborated the formation of an unexpected 1,4-diketo tautomeric form of 2-hydroxyhydronaphthoquinone as a stable intermediate. Similar 1,4-diketo tautomers of hydronaphthoquinones were established as products of the NADPH-dependent enzymatic reduction of other 1,4-naphthoquinones, and as substrates for different members of the superfamily of short-chain dehydrogenases. We propose an essential role of hydroquinone diketo tautomers in biosynthesis and detoxification processes.


dearomatization; diversity-oriented synthesis; enzyme catalysis; hydroquinones; reaction mechanisms

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