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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Biosynthesis of the africane-type sesquiterpenoid ophioceric acid involves a cytochrome P450 mediated enone formation
1State Key Laboratory of Microbial Metabolism, Joint International Research Laboratory on Metabolic & Developmental Sciences, and School of Life Sciences & Biotechnology, Shanghai Jiao Tong University, Shanghai 200240, China; Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai 201203, China.
Abstract:
Ophioceric acid (1) is a representative member of africane-type sesquiterpenoids featured with a 5/7/3 tricyclic skeleton. Guided by retrobiosynthesis, we mined the biosynthetic gene cluster of 1 from the fungus Trichoderma harzianum. Based on the results from both in vivo and in vitro studies, the biosynthesis of 1 was elucidated. A class I sesquiterpenoid cyclase OphA catalyzes the formation of africanol (2) from farnesyl-diphosphate. And the conversion of 2 to 1 is catalyzed by two cytochrome P450s, via a P450 mediated enone formation and a P450 catalyzed functionalization of a methyl group to a carboxylic acid.
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