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Photoexcitation of flavoenzymes enables a stereoselective radical cyclization
Ist Teil von
Science (American Association for the Advancement of Science), 2019-06, Vol.364 (6446)
Ort / Verlag
United States: AAAS
Erscheinungsjahr
2019
Quelle
Science Online_科学在线
Beschreibungen/Notizen
Photoexcitation is a common strategy for initiating radical reactions in chemical synthesis. We found that photoexcitation of flavin-dependent “ene”-reductases changes their catalytic function, enabling these enzymes to promote an asymmetric radical cyclization. This reactivity enables the construction of five-, six-, seven-, and eight-membered lactams with stereochemical preference conferred by the enzyme active site. After formation of a prochiral radical, the enzyme guides the delivery of a hydrogen atom from flavin—a challenging feat for small-molecule chemical reagents. The initial electron transfer occurs through direct excitation of an electron donor-acceptor complex that forms between the substrate and the reduced flavin cofactor within the enzyme active site. As a result, photoexcitation of promiscuous flavoenzymes has thus furnished a previously unknown biocatalytic reaction.
Sprache
Englisch
Identifikatoren
ISSN: 0036-8075
eISSN: 1095-9203
DOI: 10.1126/science.aaw1143
Titel-ID: cdi_osti_scitechconnect_1529103
Format
–
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