286-45-3Relevant academic research and scientific papers
Highly efficient aerobic epoxidation of cyclic olefins in mild conditions by a novel binuclear manganese(II) complex containing N-(4-nitrophenyl)picolinamide ligand
Bagherzadeh, Mojtaba,Ghanbarpour, Alireza,Khavasi, Hamid Reza
, p. 72 - 75 (2015)
A novel binuclear Mn(II) complex based on a para-nitro substituted amidic ligand (N-(4-nitrophenyl)picolinamide) has been synthesized and characterized by X-ray crystallography. This complex shows a high degree of conversion and epoxide selectivity in Mukaiyama aerobic epoxidation reactions of cyclic olefins in mild conditions.
The enhanced catalytic activity and stability of oxodiperoxomolybdenum- modified mesoporous organosilicas in selective epoxidation reactions
Shylesh, Sankaranarayana Pillai,Jia, Mingjun,Seifert, Andreas,Adappa, Sridhar,Ernst,Thiel, Werner R.
, p. 717 - 719 (2009)
Complexes of the type (L-L)MoO(O2)2 heterogenized on phenylene-bridged mesoporous organosilicas show a 10-fold increase in catalytic activity and a high stability in liquid phase epoxidation reactions, with H 2O2 as the oxidant, compared to the corresponding MCM-41-derived systems.
Multilayer structured MFI-type titanosilicate: Synthesis and catalytic properties in selective epoxidation of bulky molecules
Wang, Jianggan,Xu, Le,Zhang, Kun,Peng, Honggen,Wu, Haihong,Jiang, Jin-Gang,Liu, Yueming,Wu, Peng
, p. 16 - 23 (2012)
A lamellar titanosilicate (LTS-1) was hydrothermally synthesized by employing a bifunctional surfactant as the structure-directing agent (SDA). Highly crystalline LTS-1 was obtained at an optimal SDA/Si molar ratio of 0.04. As-synthesized LTS-1 possessed a multilayer structure, which was constructed from a collection of 2-nm zeolite nanosheets and interlayer SDA molecules. Removing the intercalated organic species induced irregular layer stacking to a certain extent, leading to intracrystal mesopores of ca. 3.2 nm in diameter. The catalytic performance of LTS-1 was investigated in the epoxidation of various bulky alkenes with tert-butyl hydroperoxide, cumene hydroperoxide, or aqueous H2O2. LTS-1 was more active than conventional titanosilicates for reactions involving bulky alkenes and oxidants, and it was immune to Ti leaching and irreversible deactivation.
Selective epoxidation of alkenes using highly active V-SBA-15 materials: Microwave vs. conventional heating
Jurado, Maria Jose,Gracia, Maria Dolores,Campelo, Juan Manuel,Luque, Rafael,Marinas, Jose Maria,Romero, Antonio Angel
, p. 8603 - 8609 (2009)
V-SBA-15 materials prepared using a hydrothermal methodology were found to be highly active and selective in the oxidation of a range of alkanes under mild reaction conditions. The activities of the systems were compared under conventional and microwave heating. Microwave experiments demonstrated that the long times of reaction (12-24 h) required under conventional heating could be reduced to a few minutes (15-60) with improved activities and selectivities under similar reaction conditions. The Royal Society of Chemistry 2009.
Proton Switch in the Secondary Coordination Sphere to Control Catalytic Events at the Metal Center: Biomimetic Oxo Transfer Chemistry of Nickel Amidate Complex
Kim, Soohyung,Jeong, Ha Young,Kim, Seonghan,Kim, Hongsik,Lee, Sojeong,Cho, Jaeheung,Kim, Cheal,Lee, Dongwhan
supporting information, p. 4700 - 4708 (2021/02/12)
High-valent metal-oxo species are key intermediates for the oxygen atom transfer step in the catalytic cycles of many metalloenzymes. While the redox-active metal centers of such enzymes are typically supported by anionic amino acid side chains or porphyrin rings, peptide backbones might function as strong electron-donating ligands to stabilize high oxidation states. To test the feasibility of this idea in synthetic settings, we have prepared a nickel(II) complex of new amido multidentate ligand. The mononuclear nickel complex of this N5 ligand catalyzes epoxidation reactions of a wide range of olefins by using mCPBA as a terminal oxidant. Notably, a remarkably high catalytic efficiency and selectivity were observed for terminal olefin substrates. We found that protonation of the secondary coordination sphere serves as the entry point to the catalytic cycle, in which high-valent nickel species is subsequently formed to carry out oxo-transfer reactions. A conceptually parallel process might allow metalloenzymes to control the catalytic cycle in the primary coordination sphere by using proton switch in the secondary coordination sphere.
Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide
Kokotos, Christoforos G.,Kokotou, Maroula G.,Lotter, Dominik,Sparr, Christof,Triandafillidi, Ierasia
, p. 10191 - 10196 (2021/08/12)
The organocatalytic epoxidation of unactivated alkenes using aqueous hydrogen peroxide provides various indispensable products and intermediates in a sustainable manner. While formyl functionalities typically undergo irreversible oxidations when activating an oxidant, an atropisomeric two-axis aldehyde capable of catalytic turnover was identified for high-yielding epoxidations of cyclic and acyclic alkenes. The relative configuration of the stereogenic axes of the catalyst and the resulting proximity of the aldehyde and backbone residues resulted in high catalytic efficiencies. Mechanistic studies support a non-radical alkene oxidation by an aldehyde-derived dioxirane intermediate generated from hydrogen peroxide through the Payne and Criegee intermediates.
Nonheme manganese(III) complexes for various olefin epoxidation: Synthesis, characterization and catalytic activity
Lee, Sojeong,Park, Soyoung,Lee, Myoung Mi,Lee, Jiyoung,Kim, Cheal
, (2021/03/14)
Three mononuclear imine-based non-heme manganese(III) complexes with tetradentate ligands which have two deprotonated phenolate moieties, ([(X2saloph)Mn(OAc)(H2O)], 1a for X = Cl, 1b for X = H, and 1c for X = CH3, saloph = N,N-o-phenylenebis(salicylidenaminato)), were synthesized and characterized by 1H NMR, 13C NMR, ESI-Mass and elemental analysis. MnIII complexes catalysed efficiently various olefin epoxidation reactions with meta-chloroperbenzoic acid (MCPBA) under the mild condition. MnIII complexes 1a and 1c with the electron-withdrawing group -Cl and electron-donating group –CH3 showed little substituent effect on the epoxidation reactions. Product analysis, Hammett study and competition experiments with cis- and trans-2-octene suggested that MnIV = O, MnV = O, and MnIII-OOC(O)R species might be key oxidants in the epoxidation reaction under this catalytic system. In addition, the use of PPAA as a mechanistic probe demonstrated that Mn-acylperoxo intermediate (MnIII-OOC(O)R) 2 generated from the reaction of peracid with manganese complexes underwent both the heterolysis and the homolysis to produce MnV = O (3) or MnIV = O species (4). Moreover, the MnIII-OOC(O)R 2 species could react directly with the easy-to-oxidize substrate to give epoxide, whereas the species 2 might not be competent to the difficult-to-oxidize substrate for the epoxidation reaction.
Rational Construction of an Artificial Binuclear Copper Monooxygenase in a Metal-Organic Framework
Feng, Xuanyu,Song, Yang,Chen, Justin S.,Xu, Ziwan,Dunn, Soren J.,Lin, Wenbin
supporting information, p. 1107 - 1118 (2021/01/25)
Artificial enzymatic systems are extensively studied to mimic the structures and functions of their natural counterparts. However, there remains a significant gap between structural modeling and catalytic activity in these artificial systems. Herein we report a novel strategy for the construction of an artificial binuclear copper monooxygenase starting from a Ti metal-organic framework (MOF). The deprotonation of the hydroxide groups on the secondary building units (SBUs) of MIL-125(Ti) (MIL = Matériaux de l'Institut Lavoisier) allows for the metalation of the SBUs with closely spaced CuI pairs, which are oxidized by molecular O2 to afford the CuII2(μ2-OH)2 cofactor in the MOF-based artificial binuclear monooxygenase Ti8-Cu2. An artificial mononuclear Cu monooxygenase Ti8-Cu1 was also prepared for comparison. The MOF-based monooxygenases were characterized by a combination of thermogravimetric analysis, inductively coupled plasma-mass spectrometry, X-ray absorption spectroscopy, Fourier-transform infrared spectroscopy, and UV-vis spectroscopy. In the presence of coreductants, Ti8-Cu2 exhibited outstanding catalytic activity toward a wide range of monooxygenation processes, including epoxidation, hydroxylation, Baeyer-Villiger oxidation, and sulfoxidation, with turnover numbers of up to 3450. Ti8-Cu2 showed a turnover frequency at least 17 times higher than that of Ti8-Cu1. Density functional theory calculations revealed O2 activation as the rate-limiting step in the monooxygenation processes. Computational studies further showed that the Cu2 sites in Ti8-Cu2 cooperatively stabilized the Cu-O2 adduct for O-O bond cleavage with 6.6 kcal/mol smaller free energy increase than that of the mononuclear Cu sites in Ti8-Cu1, accounting for the significantly higher catalytic activity of Ti8-Cu2 over Ti8-Cu1.
PEPTIDE CONJUGATES OF CYTOTOXINS AS THERAPEUTICS
-
Paragraph 0448-0449, (2021/01/25)
The present invention relates to peptide conjugates of cytotoxins such as topoisomerase I inhibitors which are useful for the treatment of diseases such as cancer.
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.
