Reaction Mechanism of a Nonheme Iron Enzyme Catalyzed Oxidative Cyclization via C–C Bond Formation

A complementary study including design of mechanistic probes, biochemical assays, model analysis, and liquid chromatography coupled mass spectrometry was conducted to establish the reaction mechanism for a nonheme iron enzyme catalyzed (−)-podophyllotoxin formation. Our results indicate that the ori...

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Bibliographic Details
Published in:Organic letters 2019-01, Vol.21 (1), p.228-232
Main Authors: Chang, Wei-chen, Yang, Zhi-Jie, Tu, Yueh-Hua, Chien, Tun-Cheng
Format: Article
Language:English
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Summary:A complementary study including design of mechanistic probes, biochemical assays, model analysis, and liquid chromatography coupled mass spectrometry was conducted to establish the reaction mechanism for a nonheme iron enzyme catalyzed (−)-podophyllotoxin formation. Our results indicate that the originally proposed hydroxylated intermediate is unlikely to be involved in this reaction. Instead, the formation of benzylic radical/carbocation intermediate can be utilized to trigger the C–C bond formation to construct the C-ring of (−)-podophyllotoxin.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.8b03670