Elucidation of Relative and Absolute Configurations of Highly Rearranged Diterpenoids and Evidence for a Putative Biosynthetic Intermediate from the Australian Nudibranch Goniobranchus geometricus

J Nat Prod. 2019 Mar 22;82(3):449-455. doi: 10.1021/acs.jnatprod.8b00713. Epub 2018 Nov 12.

Abstract

A diterpene (1), previously isolated from a Japanese marine sponge, together with two undescribed (2, 3) diterpenes with highly rearranged carbon skeletons have been characterized from the Australian nudibranch species Goniobranchus geometricus. The structures and relative configuration were determined by spectroscopic analyses informed by detailed molecular modeling, as well as by DFT, DP4, and coupling constant predictions. A 13 R,14 R configuration was determined for secoshahamin (1) by chemical correlation with 12-desacetoxyshahamin C (4) and 12-desacetoxypolyrhaphin A (5); each metabolite (1, 4, and 5) was subjected to saponification and lactonization, yielding the same δ-lactone product (6). Secoshahamin has the same carbon skeleton as a putative precursor that may play a key role in the biosynthesis of highly rearranged diterpenoid scaffolds via C-9/C-11 cleavage of a spongian diterpene precursor.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Biosynthetic Pathways
  • Carbon-13 Magnetic Resonance Spectroscopy
  • Diterpenes / chemistry*
  • Diterpenes / metabolism
  • Gastropoda / metabolism*
  • Molecular Structure
  • Proton Magnetic Resonance Spectroscopy

Substances

  • Diterpenes