Hyperforones A–C, benzoyl-migrated [5.3.1]-type polycyclic polyprenylated acylphloroglucinols from Hypericum forrestii

Three unprecedented benzoyl-migrated polycyclic polyprenylated acylphloroglucinols (PPAPs), hyperforones A–C (1–3), were isolated from Hypericum forrestii, together with a new benzoyl-substituted analogue (4) of hyperforin. Compounds 1–3 are the first examples of naturally occurring benzoyl-PPAPs wi...

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Published in:Organic chemistry frontiers an international journal of organic chemistry 2020-05, Vol.7 (9), p.1070-1076
Main Authors: Wei-Jia, Lu, Wen-Jun, Xu, Yan-Qiu, Zhang, Yi-Ran, Li, Zhou, Xin, Qi-Ji, Li, Zhang, Hao, Luo, Jun, Ling-Yi, Kong
Format: Article
Language:English
Subjects:
Chirality
Circular dichroism
Computer applications
Cytotoxicity
Dichroism
Excitons
Hypericum
Magnetic resonance spectroscopy
Mathematical analysis
NMR
NMR spectroscopy
Nuclear magnetic resonance
Organic chemistry
Spectrum analysis
Substitutes
Toxicity
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Summary:Three unprecedented benzoyl-migrated polycyclic polyprenylated acylphloroglucinols (PPAPs), hyperforones A–C (1–3), were isolated from Hypericum forrestii, together with a new benzoyl-substituted analogue (4) of hyperforin. Compounds 1–3 are the first examples of naturally occurring benzoyl-PPAPs with a unique C-1 H-substituted bicyclo[5.3.1]hendecane scaffold. Their structures and absolute configurations were established by HRESIMS, NMR spectroscopy data, electronic circular dichroism (ECD) exciton chirality method, ECD calculations, and gauge-independent atomic orbital (GIAO) NMR calculations with DP4+ analyses. A plausible biosynthetic formation of the benzoyl-migrated C-1 H-substituted bicyclo[5.3.1]hendecane skeleton in 1–3via a sterically favored hemiketalization/Retro-Claisen cascade was proposed. Bzhyperforin (4) showed significant cytotoxicity against MDA-MB-231 cells with an IC50 value of 6.88 ± 1.37 μM.
ISSN:2052-4110
2052-4110
DOI:10.1039/d0qo00152j