Isolation and Absolute Configurations of Diversiform C17, C21 and C25 Terpenoids from the Marine Sponge Cacospongia sp.

Abstract

Chemical investigation of MeOH extract of a South China Sea sponge Cacospongia sp. yielded 15 terpenoids belonging to three different skeleton-types, including the unusual C17 γ-lactone norditerpenoids (1–3), the rare C21 pyridine meroterpenoid (7), and the notable C25 manoalide-type sesterterpenoids (4–6, 8–10). Compounds 1–5 were initially obtained as enantiomers, and were further separated to be optically pure compounds (1a, 1b, 2a, 2b, 3a-r, 3b-r, 4a, 4b, 5a and 5b) by chiral HPLC, with a LiAlH4 reduction aid for 3. Compounds 3a/3b (a pair of inseparable enantiomers), 4a, 5a, 6, and 7 were identified as new compounds, while 1a/1b and 2a/2b were obtained from a natural source and were determined for their absolute configurations for the first time. This is also the first time to encounter enantiomers of the well-known manoalide-type sesterterpenoids from nature. The structures with absolute configurations of the new compounds were unambiguously determined by comprehensive methods including HR-ESI-MS and NMR data analysis, optical rotation comparison, experimental and calculated electronic circular dichroism (ECD), and Mo2(OAc)4 induced circular dichroism (ICD) methods. The cytotoxicity of the isolates against selected human tumor cell lines was evaluated, however, the tested compounds showed no activity against selected cell lines.

Meroterpenoids: A Comprehensive Update Insight on Structural Diversity and Biology

“…The standard drugs used in these assays were vancomycin (MIC = 0.27 µM) for S. aureus and amphotericin B (MIC = 0.084 µM) for C. albicans. Zhang et al [81] isolated an unusual C21 pyridine bearing meroterpenoid 247 from the sponge Cacospongia sp.…”

Natural Enantiomers: Occurrence, Biogenesis and Biological Properties

“…The following supporting information can be downloaded at: Tables S1−S34 contain names, source species and references of all collected enantiomers. Refs [312][313][314][315][316] are cited in the Supplementary Materials.…”