Complex Polypropionates from a South China Sea Photosynthetic Mollusk: Isolation and Biomimetic Synthesis Highlighting Novel Rearrangements.
Angew Chem Int Ed Engl
; 59(29): 12105-12112, 2020 07 13.
Article
in En
| MEDLINE
| ID: mdl-32277730
ABSTRACT
Placobranchus ocellatus is well known to produce diverse and complex γ-pyrone polypropionates. In this study, the chemical investigation of P. ocellatus from the South China Sea led to the discovery and identification of ocellatusonesâ
A-D, a series of racemic non-γ-pyrone polyketides with novel skeletons, characterized by a bicyclo[3.2.1]octane (1, 2), a bicyclo[3.3.1]nonane (3) or a mesitylene-substituted dimethylfuran-3(2H)-one core (4). Extensive spectroscopic analysis, quantum chemical computation, chemical synthesis, and/or X-ray diffraction analysis were used to determine the structure and absolute configuration of the new compounds, including each enantiomer of racemic compounds 1-4 after chiral HPLC resolution. An array of new and diversity-generating rearrangements is proposed to explain the biosynthesis of these unusual compounds based on careful structural analysis and comparison with six known co-occurring γ-pyrones (5-10). Furthermore, the successful biomimetic semisynthesis of ocellatusoneâ
A (1) confirmed the proposed rearrangement through an unprecedented acid induced cascade reaction.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Propionates
/
Biomimetics
/
Mollusca
Limits:
Animals
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2020
Document type:
Article
Affiliation country:
China