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Computed Regioselectivity and Conjectured Biological Activity of Ene Reactions of Singlet Oxygen with the Natural Product Hyperforin
Author(s) -
Abramova Inna,
Rudshteyn Benjamin,
Liebman Joel F.,
Greer Alexander
Publication year - 2017
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/php.12706
Subject(s) - singlet oxygen , ene reaction , hyperforin , chemistry , regioselectivity , singlet state , prenylation , oxygen , stereochemistry , computational chemistry , photochemistry , organic chemistry , hypericum perforatum , catalysis , excited state , medicine , physics , enzyme , nuclear physics , pharmacology
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.