Computed Regioselectivity and Conjectured Biological Activity of Ene Reactions of Singlet Oxygen with the Natural Product Hyperforin |
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Authors: | Inna Abramova Benjamin Rudshteyn Joel F Liebman Alexander Greer |
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Institution: | 1. Department of Chemistry, Graduate Center, City University of New York, Brooklyn College, Brooklyn, NY;2. Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD |
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Abstract: | Hyperforin is a constituent of St. John's wort and coexists with the singlet oxygen sensitizer hypericin. Density functional theory, molecular mechanics and Connolly surface calculations show that accessibility in the singlet oxygen “ene” reaction favors the hyperforin “southwest” and “southeast” prenyl (2‐methyl‐2‐butenyl) groups over the northern prenyl groups. While the southern part of hyperforin is initially more susceptible to oxidation, up to 4 “ene” reactions of singlet oxygen can take place. Computational results assist in predicting the fate of adjacent hydroperoxides in hyperforin, where the loss of hydrogen atoms may lead to the formation of a hydrotrioxide and a carbonyl instead of a Russell reaction. |
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