Antifeedant and Cytotoxic Activity of Longipinane Derivatives

Abstract

The polyoxygenated longipinane derivatives 1- 8 were tested as antifeedant compounds against the herbivorous insects Spodoptera littoralis, Rhopalosiphum padi, and Myzus persicae. Compounds 1-3 and 8 exhibited significant antifeedant activity against S. littoralis and M. persicae. The antifeedant activity against S. littoralis increased moderately after the C-8 hydroxy group in 3 was removed to afford 1 and increased strongly after the remaining two hydroxy groups were acetylated to afford 2. Compound 1 was active on M. persicae. Compounds 1, 3, and 4, with an unsaturated six-membered ring, exhibited an increase in post-ingestive effects on S. littoralis ranging from antifeedant in the case of 1 to toxic for compounds 3 and 4. These compounds did not have any phytotoxic effect on Lactuca sativa. When tested on a panel of tumoral cells, compounds 2 and 6 exhibited moderate selective cytotoxic effects on the p53 null lung carcinoma cells H1299, which were not affected by the drug paclitaxel. In addition, vibrational circular dichroism (VCD) was applied to the representative longipinene derivative 2 to verify its absolute configuration, and the sensitivity of the VCD methodology was evaluated by comparing spectra of the three diastereoisomers (4 R,5 S,7 R,9 R,10 R,11 R)-7,9-diacetyloxylongipin-2-en-1-one (2), (4 R,5 S,7 S,9 R,10 R,11 R)-7,9-diacetyloxylongipin-2-en-1-one, and (4 R,5 S,7 R,9 S,10 R,11 R)-7,9-diacetyloxylongipin-2-en-1-one.

Recent advances in the use of vibrational chiroptical spectroscopic methods for stereochemical characterization of natural products

“…92 This work points out the importance of taking solvent effects into account in the calculations by using a continuum model. 102 The structure of the sesquiterpene (À)-epi-presilphiperfolan-1-ol isolated from Anemia tomentosa was reassigned to (À)-9-epi-presilphiperfolan-1-ol (45) and its absolute conguration was established as 1S,4S,7R,8R,9S using VCD spectroscopy and DFT (B3LYP/DGDZVP) calculations. 93 Conformational exibility of (S)-(À)-perillaldehyde (38), a secondary metabolite and atmospheric pollutant, was also investigated using experimental and theoretical VCD.…”

“…The rst compound of this class investigated using VCD and DFT calculations was the norlignan (+)-nyasol (102), reported from Asparagus africanus. Compound 102, which is among the most exible small organic molecules studied by VCD spectroscopy, was assigned as S aer comparison of observed VCD, both in solution and KBr pellets, with calculated (B3LYP/aug-cc-pVDZ) data.…”

Vibrational Circular Dichroism Discrimination of Diastereomeric Cedranol Acetates

“…Moreover, the 6R-cedrol and 6S-isocedrol distinction using IR spectroscopy solely was not possible, likely due to their stereo resemblances, since these epimers vary in the AC of one chiral center among the other four. VCD has been successfully employed to distinguish diastereomers in a number of cases that, summarized by the number of recognized chiral centers from their multiple chiral centers structures, are as follows: one chiral center within two, [20][21][22] within three, 23 within four, [24][25][26] within five, 19,27 within six, 28 within nine, 29 within ten 30 ; two chiral centers within four, 24,25,31 within five, 32 within seven 33 ; three chiral centers within four, 24,25 and within five, 32 and the theoretical distinction of epimers or inverse epimers. 34 Nevertheless, VCD in isolation could not unequivocally distinguish the AC of diastereomeric esters of hibiscus and garcinia acids.…”

Identification of volatile compounds and odour activity values in quinoa porridge by gas chromatography–mass spectrometry

“…Longifolenaldehyde was absent from the porridge of 17 quinoa varieties and high in nine varieties ( P < 0.05), which has been reported to be the major aroma component of cardamom oil . ( E )‐Longipinane was highest in Q7 ( P < 0.05) and may function as an anti‐feedant compound for repelling herbivorous insects . Isoaromadendrene epoxide was reported to be the main aroma component in the dried and fresh patchouli leaves, and was found at high levels from the porridge of 12 varieties, except for Q4, Q21 and Q85 ( P < 0.05).…”

“…24 (E)-Longipinane was highest in Q7 (P < 0.05) and may function as an anti-feedant compound for repelling herbivorous insects. 25 Isoaromadendrene epoxide was reported to be the main aroma component in the dried and fresh patchouli leaves, 26 and was found at high levels from the porridge of 12 varieties, except for Q4, Q21 and Q85 (P < 0.05). (E,E)-2,4-Heptadienal was released from the porridge of all varieties, although only at a low concentration, apart from in Q106.…”