Academic literature on the topic 'Guaiane sesquiterpenoids'

Daphnauranins C–E (compounds 1–3), two sesquiterpenoids and one monoterpenoid were isolated from the roots of Daphne aurantiaca Diels. Daphnauranin C is a 9-O-13 etherified and hydroperoxy-substituted guaiane sesquiterpenoid, daphnauranin D is a guaiane sesquiterpenoid ketal, and daphnauranin E is a monoterpenoid lactone. Their structures were elucidated by comprehensive analyses of MS, 1D NMR, and 2D NMR spectroscopic data. In an anti-feeding activities test, daphnauranins C–E showed activity against male fruit fly with anti-feeding indexes (AI) up to 39.1, 39.2, and 27.8% respectively, at 1 mM.

Two new guaiane sesquiterpenoids named jatrophaols A and B (1, 2), along with three known analogues, were isolated from the roots of Jatropha curcas. Their structures were determined by spectroscopic methods, including 1D and 2D NMR spectroscopy, HR-EI-MS, HR-ESI-MS, and X-ray diffraction, as well as by comparison of their spectral data with those of related compounds.

Two new guaiane derivatives (1 and 2) along with six known sesquiterpenoids (3-8) were isolated from the gorgonian Menella woodin. Their structures were elucidated by ID and 2D NMR and HRESIMS data as well as by comparison of their spectra with those in the literature. Relative configurations of asymmetric centers in 1 and 2 were suggested on the basis of NOESY and ID NOE correlations, absolute stereochemistry of these compounds was proposed in result of comparison of calculated (for both enatiomers) and experimental ECD. Some suggestions were made regarding a biosynthesis of guaiane sesquiterpenoids in this species. All the compounds were firstly isolated from M woodin.

This study investigated the protective effects of guaiane-type sesquiterpenoids isolated from Dendranthema morifolium (Ramat.) S. Kitam flowers on lipopolysaccharide (LPS)-induced injury in H9c2 cardiomyocyte. Cell viability was determined by thiazolyl blue tetrazolium bromide (MTT). The content of released tumor necrosis factor alpha (TNF- α) and interleukin 6 (IL-6) was evaluated by enzyme-linked immunosorbent assay. The levels of lactate dehydrogenase (LDH) and creatine phosphate kinase (CK) were measured by using commercial available kits. The protein expression levels of pelF2 α, GRP78, Bax, caspase-3, caspase-9, Bcl-2, LC3-II, and p62 were measured by in-cell Western. Flow cytometry was used to detect H9c2 cardiomyocyte apoptosis. Compounds 5, 7, 1, 8, and 2 exhibited the effects of cardioprotection and activity sequence enhancement. The levels of IL-6, TNF- α, LDH, CK, pelF2 α, GRP78, Bax, caspase-3, caspase-9, p62, and H9c2 cardiomyocyte apoptosis were increased in LPS-treated H9c2 cardiomyocyte, while those of Bcl-2 and LC3-II were decreased. These effects could be effectively reversed by compounds 5, 7, 1, 8, and 2. Results demonstrated that the guaiane-type sesquiterpenoids could prevent LPS-induced injury in cardiomyocyte by decreasing endoplasmic reticulum (ER) stress, apoptosis, and autophagy as well as downregulating the inflammatory mediators. In addition, the active groups of guaiane-type sesquiterpenoids might be the angelate at C-8 and the exocyclic double bond at C-11.

The work within this thesis is positioned in the field of natural product (NP) chemistry and covers three main integrated studies along with some additional explorations. These studies not only included the isolation and characterisation of NP but also involved total syntheses of various NP and related derivatives and detailed mechanistic studies into potential routes of formation in nature. Given my naturally emerging zest for natural products, I have begun this thesis with a detailed discussion of the numerous syntheses of Taxol. This exemplar highlights not only why the field of natural products is so important, but also highlights the ever growing significance of total and semi-syntheses. The first major study investigated the phenolic profile and antioxidant activity of the leaves of the Australian native plant Smilax glyciphylla. Along with the sweet principle glycyphyllin A, seven phenolic compounds including two new dihydrochalcone rhamnosides, glycyphyllin B and C, and five known flavonoids were isolated from the ethanolic extract of the leaves of Smilax glyciphylla for the first time. The structures of these compounds were characterised by spectroscopic methods including UV, HRMS, 1D and 2D NMR. In vitro antioxidant capacity tests employing the FRAP and DPPH assays indicated that three of the isolated compounds exhibited potent antioxidant activity and are the key phenolics responsible for the high antioxidant activity of the leaf extract of S. glyciphylla. The second major study focused on the synthesis of guaiane type sesquiterpenoids via the diastereoselective epoxidation of guaiol and realized by manipulating the types of remote protecting groups on the isopropanoyl side chain, choice of solvent and epoxidising reagent. This stragety allowed for a concise stereoselective synthesis of a range of guaiane-type sesquiterpenoids including the natural products guaia-4(5)-en-11-ol, guaia-5(6)-en-11-ol, and aciphyllene and epimers of the recently isolated natural products, 1-epi-guaia-4(5)-en-11-ol, 1-epi-aciphyllene and 1-epi-melicodenone C and E in up to 31% yield within 11 steps. The third study explored the autoxidation of α-guaiene and the mechanisms involved. Over a dozen sesquiterpenoids including natural rotundone, corymbolone and the C7 epimers of natural chabrolidione A and several unstable hydroperoxide intermediates were isolated from the autoxidation products of α-guaiene. Their structures were elucidated on the basis of spectroscopic data along with the synthesis of authentic compounds. Detailed mechanistic studies have allowed many of the mechanisms involved in the formation of these downstream oxidation products to be elucidated. Together with the above main studies, several deuterium labelled precursors including d₇-α- guaiene, d₅-(2R/2S)-rotundols, d₅-α-bulnesone, d₇-α-bulnesene and d₅-2R-bulnesol were synthesised and used as internal standards to develop a robust analytical method (SIDA) to monitor the transformation of certain precursors to the sesquiterpneoid fragrances rotundone and 2R-bulnesol. A total of five publications support my research works herein and are included as the main research chapters of this thesis.
Thesis (Ph.D.) -- University of Adelaide, School of Agriculture, Food and Wine, 2014