Elsevier

Tetrahedron Letters

Volume 58, Issue 22, 31 May 2017, Pages 2113-2117
Tetrahedron Letters

seco-Polycyclic polyprenylated acylphloroglucinols with unusual carbon skeletons from Hypericum ascyron

https://doi.org/10.1016/j.tetlet.2017.04.044Get rights and content

Highlights

  • Polyprenylated acylphloroglucinols, ascyronones A–D, were isolated from Hypericum ascyron.

  • Compounds 1 and 2 shared an unusual seven-membered carbon core fused with a γ-lactone ring.

  • A biomimetic transformation from hyperibone J (5) to ascyronone A (1) was performed.

  • All the isolates were decorated with a methyl group at C-5 instead of a prenyl or geranyl group.

Abstract

Three new seco-polycyclic polyprenylated acylphloroglucinols (PPAPs), ascyronones A–C (13), and a new biosynthetic precursor, ascyronone D (4), were isolated from Hypericum ascyron together with three known analogues (57). Compounds 1 and 2, sharing an unusual seven-membered carbon core fused with a γ-lactone ring, could be derived from 1,9-seco-PPAPs via further rearrangement. A biomimetic transformation from 5 to 1 was performed by using base-driven retro-Claisen and rearrangement cascade reaction, which further confirmed the structure of 1 and shed light to its possible biosynthetic pathway. Interestingly, all these compounds are decorated with a methyl group at C-5 instead of a prenyl or geranyl group in many other PPAPs. The isolates were evaluated for their inhibitory activities against five human tumor cell lines.

Section snippets

Acknowledgments

The work was financially supported by the Natural Sciences Foundation of Yunnan Province (No. 2015FA032, 2016FB017), Foundation of Kunming Institute of Botany (P2015-ZZ07 and KIB2017001), the Foundation from Youth Innovation Promotion Association CAS to X.W.Y. (2016350), and the West Light Foundation of the Chinese Academy of Sciences to X.W.Y.

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