57717-97-2Relevant academic research and scientific papers
Exploring the substrate specificity of Cytochrome P450cin
Stok, Jeanette E.,Giang, Peter D.,Wong, Siew Hoon,De Voss, James J.
, (2019/08/02)
Cytochromes P450 are enzymes that catalyse the oxidation of a wide variety of compounds that range from small volatile compounds, such as monoterpenes to larger compounds like steroids. These enzymes can be modified to selectively oxidise substrates of interest, thereby making them attractive for applications in the biotechnology industry. In this study, we screened a small library of terpenes and terpenoid compounds against P450cin and two P450cin mutants, N242A and N242T, that have previously been shown to affect selectivity. Initial screening indicated that P450cin could catalyse the oxidation of most of the monoterpenes tested; however, sesquiterpenes were not substrates for this enzyme or the N242A mutant. Additionally, both P450cin mutants were found to be able to oxidise other bicyclic monoterpenes. For example, the oxidation of (R)- and (S)-camphor by N242T favoured the production of 5-endo-hydroxycamphor (65–77% of the total products, dependent on the enantiomer), which was similar to that previously observed for (R)-camphor with N242A (73%). Selectivity was also observed for both (R)- and (S)-limonene where N242A predominantly produced the cis-limonene 1,2-epoxide (80% of the products following (R)-limonene oxidation) as compared to P450cin (23% of the total products with (R)-limonene). Of the three enzymes screened, only P450cin was observed to catalyse the oxidation of the aromatic terpene p-cymene. All six possible hydroxylation products were generated from an in vivo expression system catalysing the oxidation of p-cymene and were assigned based on 1H NMR and GC-MS fragmentation patterns. Overall, these results have provided the foundation for pursuing new P450cin mutants that can selectively oxidise various monoterpenes for biocatalytic applications.
Total Synthesis of 7-epi-Pukalide and 7-Acetylsinumaximol B
McAulay, Kirsten,Clark, J. Stephen
supporting information, p. 9761 - 9765 (2017/07/25)
Convergent total syntheses of the furanocembranoids 7-epi-pukalide and 7-acetylsinumaximol B have been achieved using a one-pot Knoevenagel condensation and thioether-mediated furan-forming reaction. Furan formation proceeds via a sulfur ylide and results
Fe/EuroPh catalysts for limonene oxidation to 1,2-epoxylimonene, its diol, carveol, carvone and perillyl alcohol
Mlodzik, Jacek,Wrblewska, Agnieszka,Makuch, Edyta,Wrbel, Rafal J.,Michalkiewicz, Beata
, p. 111 - 120 (2016/04/26)
The catalysts in the form of an activated carbon EuroPh supported Fe were prepared and characterized structurally and chemically by XRD, nitrogen sorption, FESEM, EDX, and ICP-AES methods. The active phase was magnetite Fe3O4. The concentration of Fe in the catalysts was equal to 0.68, 1.32, 2.64 wt%. The catalytic activity of the obtained catalysts was examined in limonene oxidation with hydrogen peroxide and tert-butyl hydroperoxide as oxidants. The studies were carried out in a batch reactor. The catalytic activity of the recovered catalysts was also tested. The research showed that all from the studied catalysts were active in the limonene oxidation. As a result of limonene oxidation the following products were mainly obtained: 1,2-epoxylimonene diol, carveol, carvone and perillyl alcohol - products with a great importance. The reused catalysts were characterized by considerably lover activity in the limonene oxidation than in the first run, especially when the oxidation was performed with t-butyl hydroperoxide.
The studies on the limonene oxidation over the microporous TS-1 catalyst
Wróblewska, Agnieszka,Makuch, Edyta,Miadlicki, Piotr
, p. 121 - 129 (2016/04/26)
The studies on the oxidation of limonene with 60 wt% hydrogen peroxide over the titanium silicalite TS-1 catalyst were carried out. The influence of the following parameters was examined: the temperature 0-120 °C, the molar ratio of limonene/H2O2 = 1:2-5:1, methanol concentration 60-95 wt%, TS-1 content 0.25-8 wt% and the reaction time 15 min to 11 days. The studies showed that the most beneficial conditions for the obtaining of high selectivity of 1,2-epoxylimonene, at simultaneously high values of the conversion of reactants and the efficiency of hydrogen peroxide, are as follows: the temperature 80 °C, the molar ratio of limonene/H2O2 = 1:1, the methanol concentration 80 wt%, the TS-1 content 3 wt% and the reaction time 10 days. Moreover, the research showed that the process of limonene oxidation is very complicated, because during this process also other very useful oxygenated derivatives of limonene can be obtained, for example: perillyl alcohol, carveol, carvone and 1,2-epoxylimonene diol. The studies on the reuse of the TS-1 catalyst showed that it is very stable catalyst at the studied conditions and it can be recycled to the oxidation process at least three times.
Synthesis of (+)-perillyl alcohol from (+)-limonene
Geoghegan, Kimberly,Evans, Paul
, p. 1431 - 1433 (2014/03/21)
(+)-Perillyl alcohol (1) has been synthesised in four steps and 39% overall yield from commercially available limonene oxide (4). The sequence features, as its key step, a palladium(0)-mediated transformation of a secondary allylic acetate (6) into its primary isomer (7). An application of (+)-perillyl alcohol (1) in a formal synthesis of naturally occurring (-)-mesembrine (2) and (-)-mesembranol was demonstrated.
2-CYCLOALKYL RESORCINOL CANNABINERGIC LIGANDS
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Paragraph 0218, (2014/05/07)
The present invention relates to novel 2-cycloalkyl resorcinol compounds; to pharmaceutical compositions comprising the compounds; and to methods of preparing the compounds and uses thereof. The disclosed compounds can bind to and modulate the cannabinoid
The epoxidation of limonene over the ts-1 and ti-sba-15 catalysts
Wrblewska, Agnieszka
, p. 19907 - 19922 (2015/04/21)
Limonene belongs to a group of very important intermediates used in the production of fine chemicals. This monoterpene compound can be obtained from peels of oranges or lemon which are a (biomass) waste from the orange juice industry. Thus, limonene is a renewable, easy available and a relatively cheap compound. This work presents preliminary studies on the process of limonene epoxidation over zeolite type catalysts such as: TS-1 and Ti-SBA-15. In these studies methanol was used as a solvent and as an oxidizing agent a 60 wt % hydrogen peroxide solution was applied. The activity of each catalyst was investigated for four chosen temperatures (0 ° C, 40 ° C, 80 ° C and 120 ° C). The reaction time was changed from 0.5 to 24 h. For each catalyst the most beneficial conditions (the appropriate temperature and the reaction time) have been established. The obtained results were compared and the most active catalyst was chosen. These studies have also shown different possible ways of limonene transformation, not only in the direction of 1,2-epoxylimonene and its corresponding diol, but also in direction of carveol, carvone and perillyl alcohol-compounds with a lot of applications. The possible mechanisms of formation of the allylic oxidation products were proposed.
Synthesis and catalytic properties of molybdenum(VI) complexes with tris(3,5-dimethyl-1-pyrazolyl)methane
Neves, Patricia,Gago, Sandra,Balula, Salete S.,Lopes, Andre D.,Valente, Anabela A.,Cunha-Silva, Luis,Paz, Filipe A. Almeida,Pillinger, Martyn,Rocha, Joao,Silva, Carlos M.,Gonc-Alves, Isabel S.
scheme or table, p. 3490 - 3500 (2011/07/07)
The complex [MoO2Cl{HC(3,5-Me2pz)3}] BF4 (1) (HC(3,5-Me2pz)3 = tris(3,5-dimethyl-1- pyrazolyl)methane) has been prepared and examined as a catalyst for epoxidation of olefins at 55 °C using tert-butyl hydroperoxide (TBHP) as the oxidant. For reaction of cis-cyclooctene, epoxycyclooctane is obtained quantitatively within 5 h when water is rigorously excluded from the reaction mixture. Increasing amounts of water in the reaction mixture lead to lower activities (without affecting product selectivity) and transformation of 1 into the trioxidomolybdenum(VI) complex [{HC(3,5-Me2pz)3}MoO 3] (4). Complex 4 was isolated as a microcrystalline solid by refluxing a suspension of 1 in water. The powder X-ray diffraction pattern of 4 can be indexed in the orthorhombic Pnma system, with a = 16.7349(5) A, b = 13.6380(4) A, and c = 7.8513(3) A. Treatment of 1 in dichloromethane with excess TBHP led to isolation of the symmetrical [Mo 2O4(μ2-O){HC(3,5-Me2pz) 3}2](BF4)2 (2) and unsymmetrical [Mo2O3(O2)2(μ2- O)(H 2O){HC(3,5-Me2pz)3}] (3) oxido-bridged dimers, which were characterized by single-crystal X-ray diffraction. Complex 2 displays the well-known (Mo2O5)2+ bridging structure where each dioxidomolybdenum(VI) center is coordinated to three N atoms of the organic ligand and one μ2-bridging O atom. The unusual complex 3 comprises dioxido and oxidodiperoxo molybdenum(VI) centers linked by a μ2-bridgingO atom, with the former center being coordinated to the tridentate N-ligand. The dinuclear complexes exhibit a similar catalytic performance to that found for mononuclear 1. For complexes 1 and 2 use of the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate and N-butyl-3-methylpyridinium tetrafluoroborate as solvents allowed the complexes to be completely dissolved, and in each case the catalyst and IL could be recycled and reused without loss of activity.
Reduction of carboxylic acids using esters of benzotriazole as high-reactivity intermediates
Morales-Serna, Jose Antonio,Garcia-Rios, Erendira,Bernal, Jorge,Paleo, Ehecatl,Gavino, Ruben,Cardenas, Jorge
scheme or table, p. 1375 - 1382 (2011/06/19)
Herein, we describe a simple and practical protocol for the reduction of carboxylic acids via the in situ formation of hydroxybenzotriazole esters followed by reaction with sodium borohydride to give the corresponding alcohols. The reaction proceeds with excellent yields in the presence of water. Georg Thieme Verlag Stuttgart - New York.
Photooxidation and phototoxicity of π-extended squaraines
Rapozzi, Valentina,Beverina, Luca,Salice, Patrizio,Pagani, Giorgio A.,Camerin, Monica,Xodo, Luigi E.
experimental part, p. 2188 - 2196 (2010/08/06)
This paper describes the synthesis of π-extended squaraines and their photooxidation properties and gives an in-depth characterization of these molecules as photosensitizing agents. Squaraines show a strong absorption in the tissue transparency window (600-800 nm), and upon irradiation, they undergo a photooxidation process, leading to the formation of peroxide and hydroperoxide radicals according to a type I radical chain process. Confocal laser microscopy demonstrates that the designed squaraines efficiently internalize in the cytoplasm and not in the nucleus of the cell. In the dark, they are scarcely cytotoxic, but after irradition, they promote a strong dose-dependent phototoxic effect in four different cancer cells. In HeLa and MCF-7 cells, squaraines 4 and 5, thanks to their hydrocarbon tails, associate to the membranes and induce lipid peroxidation, as indicated by a marked increase of malonyldialdehyde after photodynamic treatment, in agreement with in vitro photooxidation studies. FACS, caspase-3/7 assays and time-lapse microscopy demonstrate that the designed squaraines cause cell death primarily by necrosis.
