89064-04-0Relevant articles and documents
SYNTHETIC SPHINGOLIPID INSPIRED MOLECULES WITH HETEROAROMATIC APPENDAGES, METHODS OF THEIR SYNTHESIS AND METHODS OF TREATMENT
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Paragraph 0186; 0189, (2021/04/02)
Small molecules compounds and methods of their synthesis are provided. Formulations and medicaments are also provided that are directed to the treatment of disease, such as, for example, neoplasms, cancers, and other diseases. Therapeutics are also provided containing a therapeutically effective dose of one or more small molecule compounds, present either as pharmaceutically effective salt or in pure form, including, but not limited to, formulations for oral, intravenous, or intramuscular administration.
g-C3N4/metal halide perovskite composites as photocatalysts for singlet oxygen generation processes for the preparation of various oxidized synthons
Corti, Marco,Chiara, Rossella,Romani, Lidia,Mannucci, Barbara,Malavasi, Lorenzo,Quadrelli, Paolo
, p. 2292 - 2298 (2021/04/12)
g-C3N4/metal halide perovskite composites were prepared and used for the first time as photocatalysts forin situ1O2generation to perform hetero Diels-Alder, ene and oxidation reactions with suitable dienes and alkenes. The standardized methodology was made applicable to a variety of olefinic substrates. The scope of the method is finely illustrated and the reactions afforded desymmetrized hydroxy-ketone derivatives, unsaturated ketones and epoxides. Some limitations were also observed, especially in the case of the alkene oxidations, and poor chemoselectivity was somewhere observed in this work which is the first application of MHP-based composites forin situ1O2generation. The experimental protocol can be used as a platform to further expand the knowledge and applicability of MHPs to organic reactions, since perovskites offer a rich variety of tuning strategies which may be explored to improve reaction yields and selectivities.
Highly selective and efficient olefin epoxidation with pure inorganic-ligand supported iron catalysts
Zhou, Zhuohong,Dai, Guoyong,Ru, Shi,Yu, Han,Wei, Yongge
supporting information, p. 14201 - 14205 (2019/10/02)
Over the past two decades, there have been major developments in the transition iron-catalyzed selective oxidation of alkenes to epoxides; a common structure found in drug, isolated natural products, and fine chemicals. Many of these approaches have enabled highly efficient and selective epoxidation of alkenes via the design of specialized ligands, which facilitates to control the activity and selectivity of the reactions catalyzed by iron atom. Herein, we report the development of the olefin epoxidation with inorganic-ligand supported iron-catalysts using 30% H2O2 as an oxidant, and the mechanism is similar to iron-porphyrin type. With the catalyst 1, (NH4)3[FeMo6O18(OH)6], various aromatic and aliphatic alkenes were successfully transformed into the corresponding epoxides with excellent yields as well as chemo- and stereo-selectivity. This catalytic system possesses the advantages of being able to avoid the use of expensive, toxic, air/moisture sensitive and commercially unavailable organic ligands. The generality of this methodology is simple to operate and exhibits high catalytic activity as well as excellent stability, which gives it the potential to be used on an industrial scale, and maybe opens a way for the catalytic oxidation reaction via inorganic-ligand coordinated iron catalysis.
Design, synthesis and anticancer activity of constrained sphingolipid-phenoxazine/phenothiazine hybrid constructs targeting protein phosphatase 2A
Garsi, Jean-Baptiste,Vece, Vito,Sernissi, Lorenzo,Auger-Morin, Catherine,Hanessian, Stephen,McCracken, Alison N.,Selwan, Elizabeth,Ramirez, Cuauhtemoc,Dahal, Amogha,Romdhane, Nadine Ben,Finicle, Brendan T.,Edinger, Aimee L.
supporting information, p. 2681 - 2685 (2019/08/07)
Inspired by the cytotoxicity of perphenazine toward cancer cells and its ability to activate the serine/threonine protein phosphatase 2A (PP2A), we prepared series of ether-carbon linked analogs of a constrained synthetic sphingolipid analog 3, known for its cytotoxicity, nutrient transporter down-regulation and vacuolation properties, incorporating the tricyclic neuroleptics phenoxazine and phenothiazine to represent hybrid structures with possible synergistic cytotoxic activity. While the original activity of the lead compound 3 was diminished by fusion with the phenoxazine or phenothiazine tethered moieties, the corresponding 3-pyridyltetryl ether analog 10 showed cytotoxicity and nutrient transporter down-regulation similar to the lead compound 3, although it separated these PP2A-dependent phenotypes from that of vacuolation.
An Isolable and Bench-Stable Epoxidizing Reagent Based on Triazine: Triazox
Yamada, Kohei,Igarashi, Yuki,Betsuyaku, Tatsuki,Kitamura, Masanori,Hirata, Koki,Hioki, Kazuhito,Kunishima, Munetaka
supporting information, p. 2015 - 2019 (2018/04/16)
A new triazine-based oxidizing reagent, 2-hydroperoxy-4,6-diphenyl-1,3,5-triazine (Triazox), has been developed. The reagent can be synthesized from inexpensive starting materials and is a bench-stable solid that is isolable in pure form. Epoxidation of alkenes possessing acid-sensitive functionalities using Triazox proceeded in good to excellent yields. The accompanying nonacidic triazinone coproduct can be easily removed by filtration. These features indicate that Triazox is a practically useful oxidizing reagent.
Effect of Transition Metal Compounds on the Cyclohexene Oxidation Catalyzed by N-Hydroxyphthalimide
Kuznetsova,Kuznetsova,Yakovina,Zudin,Bal’zhinimaev
, p. 735 - 743 (2019/03/13)
Abstract: N-Hydroxyphthalimide (NHPI) is an efficient organic catalyst in the oxidation reactions of organic compounds occurring via a radical mechanism, often used together with redox-active ions or transition metal complexes. In this work the catalytic action of NHPI is studied together with Cu(II), Fe(III), and Mo(VI) compounds in the reaction of aerobic oxidation of cyclohexene in an acetonitrile solution at 60°C. It was found that iron(III) benzoate accelerates the reaction by rapidly generating the active form of the phthalimide-N-oxyl radical (PINO) catalyst, but does not cause decomposition of the hydroperoxide. The oxidation product is 2-cyclohexenyl hydroperoxide formed with a selectivity of 85% at a cyclohexene conversion of 50%. Copper(II) acetate initiates oxidation and is capable of catalyzing the radical decomposition of the hydroperoxide and secondary oxidation of allyl oxygenates. When reaching a cyclohexene conversion close to 80%, the overall selectivity to the main products, 2-cyclohexenyl hydroperoxide and 2-cyclohexen-1-on, was 70%. The addition of iron(III) and molybdenum(VI) compounds led to the intensive generation of hydroperoxide and its activation as an electrophilic reactant capable of cyclohexene epoxidation. As a result of the use of the multifunctional three-component NHPI–Mo(VI)–Fe(III) catalyst, cyclohexene oxidation by molecular oxygen occurred with the formation of epoxycyclohexane. The selectivity to the products of cyclohexene epoxidation was close to 50%, which is a value expected from theory.
Peroxotantalate-Based Ionic Liquid Catalyzed Epoxidation of Allylic Alcohols with Hydrogen Peroxide
Ma, Wenbao,Chen, Chen,Kong, Kang,Dong, Qifeng,Li, Kun,Yuan, Mingming,Li, Difan,Hou, Zhenshan
, p. 7287 - 7296 (2017/05/31)
The efficient and environmentally benign epoxidation of allylic alcohols has been attained by using new kinds of monomeric peroxotantalate anion-functionalized ionic liquids (ILs=[P4,4,4,n]3[Ta(O)3(η-O2)], P4,4,4,n=quaternary phosphonium cation, n=4, 8, and 14), which have been developed and their structures determined accordingly. This work revealed the parent anions of the ILs underwent structural transformation in the presence of H2O2. The formed active species exhibited excellent catalytic activity, with a turnover frequency for [P4,4,4,4]3[Ta(O)3(η-O2)] of up to 285 h?1, and satisfactory recyclability in the epoxidation of various allylic alcohols under very mild conditions by using only one equivalent of hydrogen peroxide as an oxidant. NMR studies showed the reaction was facilitated through a hydrogen-bonding mechanism, in which the peroxo group (O–O) of the peroxotantalate anion served as the hydrogen-bond acceptor and hydroxyl group in the allylic alcohols served as the hydrogen-bond donor. This work demonstrates that simple monomeric peroxotantalates can catalyze epoxidation of allylic alcohols efficiently.
Oxidation of olefins using molecular oxygen catalyzed by a part per million level of recyclable copper catalyst under mild conditions
Yang, Guoqiang,Du, Huiyuan,Liu, Jia,Zhou, Zheng,Hu, Xingbang,Zhang, Zhibing
, p. 675 - 681 (2017/08/14)
Copper catalysts with an imidazole salt tag ([Cu-Imace-R-H][X], X- = F-, Cl-, Br-, I-, CF3CO2-, HSO4-, NO3-, PF6- or BF4-; R = H or CH3) show quite high reactivity for the oxidation of non-aromatic olefins with good selectivity for epoxides. The reactions perform well with a part per million (ppm) catalyst loading at mild temperature and ambient pressure. The highest turnover frequency (TOF) reaches up to 900:000 h-1. The catalytic activity is easy to control by changing the anion of [Cu-Imace-R-H][X]. This catalyst is effective for a series of substrates, including internal and terminal olefins, tri- and tetra-substituted olefins and aromatic olefins. In addition, the copper catalyst can be conveniently separated from the reaction system and reused for at least six cycles without any obvious loss of catalytic activity.
Hydrogen bond donor functionalized dioxido-molybdenum(VI) complexes as robust and highly efficient precatalysts for alkene epoxidation
Zwettler, Niklas,Schachner, J?rg A.,Belaj, Ferdinand,M?sch-Zanetti, Nadia C.
, p. 209 - 219 (2017/11/15)
The synthesis of four novel, tridentate aminophenolate ligands HL1-HL4, bearing amide functionalities is reported. Reaction of these ligands with a dioxido molybdenum(VI) precursor led, depending on the choice of solvent, to mononuclear complexes of the type [MoO2L(OMe)] (2, 4, 6) or dinuclear complexes [{MoO2L}2(μ-O)] (1, 3, 5, 7), containing one facially, tridentate ONO-ligand per metal center. This synthetic discrimination between dinuclear and mononuclear complexes allows for a comparison between structures and reactivity. Complexes 1-7 were found to be highly active catalysts in the epoxidation of several internal and terminal alkenes. With tert-butyl hydroperoxide (TBHP) as oxidant, precatalyst loadings of 0.0005 mol% (5 ppm) could be realized leading to turnover numbers of up to 110000. The precatalysts also allowed for the use of hydrogen peroxide (0.1 mol% precatalyst) as oxidant as well as various alcohols as “green” solvents, such as ethanol or even tert-butanol (usually an inhibitor of epoxidation).
Heterogenization of ketone catalyst for epoxidatio by low pressure plasma fluorination of silica gel supports
D'Accolti, Lucia,De Vietro, Nicoletta,Fanelli, Fiorenza,Fusco, Caterina,Nacci, Angelo,Fracassi, Francesco
, (2018/01/03)
Low pressure plasma was used for preparing heterogeneous organocatalysts 2-(A)-(C) suitable for dioxirane-mediated epoxidations. Heterogenization was accomplished by adsorption of the methyl perfluoroheptyl ketone (2) on fluorinated supports (A)-(C) deriving from the treatment of commercial C8-silica gel in low pressure plasma fed with fluorocarbons. Catalyst 2-(C) proved to be the most efficient one, promoting epoxidation of an array of alkenes, including unsaturated fatty esters like methyl oleate (10) and the triglyceride soybean oil (11), with the cheap potassium peroxymonosulfate KHSO5 (caroate) as a green oxidant. Notably, the perfluorinated matrix gives rise to the activation of caroate, generating singlet oxygen. Materials were characterized by infrared Attenuated Total Reflectance spectroscopy (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS) and Emission Scanning Electron Microscope (FESEM).
