1. Syntheses Based on 3,4α-Epoxy-1,5,7α,6β(H)-guai-10(14),11(13)-dien-6,12-olide
Sergazy Adekenov Molecules. 2022 Mar 13;27(6):1862. doi: 10.3390/molecules27061862.
The sesquiterpene γ-lactone estafiatin 1, the molecule of which has a structure of 3,4α-epoxy-1,5,7α,6β(H)-guai-10(14),11(13)-dien-6,12-olide, is characteristic of plants of the genera Achillea L. and Artemisia L. of the Asteraceae family. This article presents the results of chemical modification for three reaction centers of the estafiatin molecule 1: epoxy cycle, exomethylene group conjugated with γ-lactone carbonyl, and exomethylene group in position C10=C14; and at the same time 33 new derivatives were synthesized, the structures of which were established based on physicochemical constants, spectral data (IR-, PMR-, 13C-NMR), and X-ray diffraction analysis. The stereo- and regiospecificity, as well as the chemoselectivity of the reaction based on estafiatin molecule 1, are discussed. The reactivity of the substrate is significantly influenced by the stereochemistry of its molecule, the nature of the reagent, and the reaction medium. Based on the results of in silico screening, derivatives of estafiatin with high binding energies for both DNA-topoisomerase I and DNA-topoisomerase II were identified. The values of the inhibitory dose of IC50 for estafiatin 1 and its derivatives were determined on cell lines of eight types of tumors. in vivo experiments of the samples made it possible to establish that estafiatin 1 and its derivatives have pronounced antitumor activity against Pliss lymphosarcoma, Walker's carcinosarcoma, sarcoma 45, sarcoma-180, alveolar liver cancer PC-1, leukemia P-388 and L-1210, and sarcoma-45 resistant to 5-fluorouracil.
2. Analysis, potency and occurrence of (Z)-6-dodeceno-γ-lactone in white wine
Tracey E Siebert, Alice Barker, Sheridan R Barter, Miguel A de Barros Lopes, Markus J Herderich, I Leigh Francis Food Chem. 2018 Aug 1;256:85-90. doi: 10.1016/j.foodchem.2018.02.094. Epub 2018 Feb 17.
(Z)-6-Dodeceno-γ-lactone is a potent aroma compound that has been little studied and its prevalence in wines is unknown. An efficient stable isotope dilution assay was developed using a simple, direct immersion solid-phase microextraction and gas chromatography-tandem mass spectrometry method suitable for routine use with a low ng/L limit of quantitation. Using this method, 99 out of 104 young white wines analysed were found to contain detectable (Z)-6-dodeceno-γ-lactone. The highest concentrations were found in Riesling and Viognier wines. (Z)-6-Dodeceno-γ-lactone was found to have an aroma detection threshold of 700 ng/L in a neutral white wine. This study established that (Z)-6-dodeceno-γ-lactone is widely present in Australia's most popular white wine varieties, but generally at concentrations below its aroma detection threshold.
3. Sesquiterpene lactone dimers from the fruit of Carpesium abrotanoides L
Yu-Fang Wang, Yan Fu, Yan-Nan Ji, Ning-Ning Shi, Francoise Sauriol, Xin-Hua Lu, Yu-Cheng Gu, Qing-Wen Shi, Chang-Hong Huo Phytochemistry. 2022 Nov;203:113389. doi: 10.1016/j.phytochem.2022.113389. Epub 2022 Aug 23.
Seven undescribed sesquiterpene lactone dimers (SLDs) (carpeabrodilactones A-G), one known SLD, and six known sesquiterpenes were isolated from the fruit of Carpesium abrotanoides L. Carpeabrodilactone A was a dimeric carabrane featuring a rare C-13-C-13' linkage. Carpeabrodilactones B and C are the first two SLDs to be described possessing a carabranolide unit and a guaianolide unit connected by an O-ether linkage. The structures of the SLDs were assigned based on HRESIMS, NMR analysis, 13C NMR calculation, ECD calculation, and modified Mosher's method. Four SLDs showed potent cytotoxicity against K562 and/or A549 cells, with IC50 values below 10 μM, but none inhibited protein tyrosine phosphatases at 40 μM, including PTP1B, SHP1, CD45, and TCPTP.
