1215-07-2Relevant articles and documents
Integrating Hydrogen Production and Transfer Hydrogenation with Selenite Promoted Electrooxidation of α-Nitrotoluenes to E-Nitroethenes
Chong, Xiaodan,Liu, Cuibo,Wang, Changhong,Yang, Rong,Zhang, Bin
supporting information, p. 22010 - 22016 (2021/09/02)
Developing an electrochemical carbon-added reaction with accelerated kinetics to replace the low-value and sluggish oxygen evolution reaction (OER) is markedly significant to pure hydrogen production. Regulating the critical steps to precisely design electrode materials to selectively synthesize targeted compounds is highly desirable. Here, inspired by the surfaced adsorbed SeOx2? promoting OER, NiSe is demonstrated to be an efficient anode enabling α-nitrotoluene electrooxidation to E-nitroethene with up to 99 % E selectivity, 89 % Faradaic efficiency, and the reaction rate of 0.25 mmol cm?2 h?1 via inhibiting side reactions for energy-saving hydrogen generation. The high performance can be associated with its in situ formed NiOOH surface layer and absorbed SeOx2? via Se leaching-oxidation during electrooxidation, and the preferential adsorption of two -NO2 groups of intermediate on NiOOH. A self-coupling of α-carbon radicals and subsequent elimination of a nitrite molecule pathway is proposed. Wide substrate scope, scale-up synthesis of E-nitroethene, and paired productions of E-nitroethene and hydrogen or N-protected aminoarenes over a bifunctional NiSe electrode highlight the promising potential. Gold also displays a similar promoting effect for α-nitrotoluene transformation like SeOx2?, rationalizing the strategy of designing materials to suppress side reactions.
Synthesis of Benzo[4,5]imidazo[2,1-b]thiazole by Copper(II)-Catalyzed Thioamination of Nitroalkene with 1H-Benzo[d]imidazole-2-thiol
Jana, Sourav,Chakraborty, Amrita,Shirinian, Valerii Z.,Hajra, Alakananda
supporting information, p. 2402 - 2408 (2018/05/08)
A Copper(II)-catalyzed thioamination of β-nitroalkene with 1H-benzo[d]imidazole-2-thiol has been developed for the synthesis of benzo[4,5]imidazo[2,1-b]thiazole derivatives. A variety of N-fused benzoimidazothiazole derivatives are obtained in high yields through successive C?N and C?S bond formations. This protocol is also applicable to β-substituted β-nitroalkenes to afford 2,3-disubstituted benzoimidazothiazoles. (Figure presented.).
Iron(III) nitrate-induced aerobic and catalytic oxidative cleavage of olefins
Amaya, Toru,Fujimoto, Hayato
supporting information, p. 2657 - 2660 (2018/06/04)
Microwave-assisted catalytic oxidative cleavage of olefins using Fe(NO3)3·9H2O under O2 is reported. This reaction system is particularly effective when 9-benzylidene-9H-fluorene derivatives are used as substrates even though they are tri- and tetra-substituted olefins.
In order to iodide is one pot synthesis nitryl source α, β - unsaturated nitro olefin derivatives (by machine translation)
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Paragraph 0122-0125; 0132-0134, (2017/09/01)
The present invention discloses a one-pot synthesis nitryl source iodide is α, β - unsaturated nitro olefin derivatives, vinyl compounds containing four aryl ferrous (III), iodide and tertiary-butyl hydrogen peroxide in acetonitrile solution system a pot of reaction, generating α, β - unsaturated nitro olefin derivatives; the method to achieve the under mild reaction conditions, high yield with high stereo selectivity of the E synthesis of α, β - unsaturated nitro olefin. (by machine translation)
Α, β - unsaturated nitro olefin derivative synthesis method (by machine translation)
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Paragraph 0027; 0034; 0124; 0126; 0133; 0134; 0135, (2017/09/05)
The invention discloses a α, β - unsaturated nitro olefin derivative synthesis method, vinyl compounds containing four aryl ferrous (III), ammonium halide and tertiary-butyl hydrogen peroxide in the system of the one-pot reaction, generating α, β - unsaturated nitro olefin derivatives; the method to achieve the under mild reaction conditions, high yield with high stereo selectivity of the E synthesis of α, β - unsaturated nitro olefin. (by machine translation)
PREPARATION OF ALDEHYDES AND KETONES FROM ALKENES USING POLYOXOMETALATE CATALYSTS AND NITROGEN OXIDES
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Paragraph 0115, (2017/03/21)
The present invention relates to a process for preparing aldehydes and ketones by carbon-carbon bond cleavage of alkenes, wherein the process is catalysed by first row transition metal nitro coordinated polyoxometalate catalyst. The catalyst can be prepared by pre-treatment of aqua coordinated polyoxometalates with NO2, or they are formed in situ when the reactions are carried in nitroalkanes under aerobic conditions, or they are formed in situ from nitrosyl (NO) compounds in the presence of O2.
Catalytic enantioselective epoxidation of nitroalkenes
Vidal-Albalat,?widerek,Izquierdo,Rodríguez,Moliner,González
supporting information, p. 10060 - 10063 (2016/08/15)
Nitroepoxides are potentially exploitable as synthons with vicinal electrophilic centers. Nevertheless, although advances have been made in the field, enantioselective epoxidation of nitroalkenes is still a challenging process. Herein we show a convenient procedure for the preparation of optically active nitroepoxides in high enantiomeric excess and high chemical yield. The kinetic data of the best catalyst have been examined using computational methods based on DFT calculations. Interestingly, the results demonstrate that the enantioselectivity of the epoxidation of nitroalkenes by this kind of catalyst is not only kinetically but also thermodynamically controlled.
K2S2O8-mediated nitration of alkenes with NaNO2 and 2,2,6,6-tetramethylpiperidine-1-oxyl: Stereoselective synthesis of (E)-nitroalkenes
Zhao, An,Jiang, Qing,Jia, Jing,Xu, Bin,Liu, Yufeng,Zhang, Mingzhong,Liu, Qiang,Luo, Weiping,Guo, Cancheng
supporting information, p. 80 - 84 (2015/12/23)
A transition-metal-free nitration of alkenes with NaNO2 in the presence of K2S2O8 and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is developed. The transformation exhibits a broad substrate scope and good functional group tolerance, thus providing a new and expedient protocol for stereoselective synthesis of (E)-nitroalkenes with moderate to good yields. Moreover, the nitration processes of (E)- and (Z)-stilbene are also studied: even though the proportion of substrates is different, the E/Z ratio of the products is basically the same. Based upon experimental observations, a possible reaction mechanism is proposed.
Aerobic carbon-carbon bond cleavage of alkenes to aldehydes catalyzed by first-row transition-metal-substituted polyoxometalates in the presence of nitrogen dioxide
Rubinstein, Amir,Jiménez-Lozanao, Pablo,Carbó, Jorge J.,Poblet, Josep M.,Neumann, Ronny
, p. 10941 - 10948 (2014/08/18)
A new aerobic carbon-carbon bond cleavage reaction of linear di-substituted alkenes, to yield the corresponding aldehydes/ketones in high selectivity under mild reaction conditions, is described using copper(II)-substituted polyoxometalates, such as {α2-Cu(L)P2W 17O61}8- or {[(Cu(L)]2WZn(ZnW 9O34)2}12-, as catalysts, where L = NO2. A biorenewable-based substrate, methyl oleate, gave methyl 8-formyloctanoate and nonanal in >90% yield. Interestingly, cylcoalkenes yield the corresponding epoxides as products. These catalysts either can be prepared by pretreatment of the aqua-coordinated polyoxometalates (L = H 2O) with NO2 or are formed in situ when the reactions are carried with nitroalkanes (for example, nitroethane) as solvents or cosolvents. Nitroethane was shown to release NO2 under reaction conditions. 31P NMR shows that the Cu-NO2-substituted polyoxometalates act as oxygen donors to the C-C double bond, yielding a Cu-NO product that is reoxidized to Cu-NO2 under reaction conditions to complete a catalytic cycle. Stoichiometric reactions and kinetic measurements using {α2-Co(NO2)P2W17O 61}8- as oxidant and trans-stilbene derivatives as substrates point toward a reaction mechanism for C-C bond cleavage involving two molecules of {α2-Co(NO2)P2W 17O61}8- and one molecule of trans-stilbene that is sufficiently stable at room temperature to be observed by 31P NMR.
