Molecular Diversity from Longipinenes of <i>Santolina viscosa</i> Lag. through Acid Catalysis: Biocidal Activity

Abstract

The search for new compounds with biocidal potential was carried out, focusing on the longipinenes 1–7 from the plant species Santolina viscosa Lag. Compounds 1, 2, and 5 showed remarkable molecular diversity when treated in acidic reaction conditions. Protonic, Lewis, and heterogeneous compounds were used in the treatment. Three main models of reaction have been observed: isomerization of the double bond (8–10); rearrangements to longibornane-based skeleton (11–15) and ring-opening to himachalane-based skeleton (16–18). Secolongibornane aldehydes 23 and 24 were obtained after epoxide opening under the same reaction conditions. The elucidation of the structures of the new compounds was carried out using spectroscopic data and was supported by computational theoretical calculations of 13C NMR spectra. Additionally, high-resolution mass spectrometry and single-crystal X-ray diffraction analysis were employed for certain compounds. Natural longipinenes 4–7, methyl esters 1–3 of corresponding natural carboxylic acids and the isomerized and derivatives compounds 8–19 exhibit moderate to high insecticidal activity against R. padi and M. persicae insects. Longipinene 5 shows potent inhibition against the root growth of the plants L. perenne and L. sativa, as well as compound 2 on the leaves of L. perenne. Furthermore, significant ixocidal and nematicidal activity was found for this latter compound.

Keywords

• natural product
• <i>Santolina viscosa</i>
• Δ⁹-longipinenes
• molecular rearrangement
• ring-opening and bioactivity