470-35-9Relevant academic research and scientific papers
EPR EVIDENCE FOR A SINGLE ELECTRON TRANSFER MECHANISM IN REACTIONS OF AROMATIC KETONES WITH LITHIUM AMIDES
Ashby, E. C.,Goel, A. B.,DePriest, R. N.
, p. 4355 - 4358 (1981)
Direct spectroscopic evidence (EPR) supporting a single electron transfer mechanism in the reaction of lithium amides with aromatic ketones is presented.
Nickel-catalyzed deoxygenation of oxiranes: Conversion of epoxides to alkenes
Mori, Takamichi,Takeuchi, Yoshihito,Hojo, Makoto
supporting information, (2020/01/24)
Deoxygenation of epoxides takes place under the catalysis of nickel in the presence of diethylzinc as a deoxygenation agent to yield alkenes. Epoxides with a wide variety of substitution patterns are deoxygenated in this catalytic system to give terminal, 1,1-disubstituted, 1,2-disubstituted, trisubstituted, and tetrasubstituted alkenes in high yields. Reactions of 1,2-disubstituted epoxides we examined proceeded in an E-stereoselective manner. High compatibility with other functional groups through this transformation was also observed.
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.
Pinacol Rearrangement and Direct Nucleophilic Substitution of Allylic Alcohols Promoted by Graphene Oxide and Graphene Oxide CO2H
Gómez-Martínez, Melania,Baeza, Alejandro,Alonso, Diego A.
, p. 1032 - 1039 (2017/03/27)
Graphene oxide (GO) and carboxylic acid functionalized GO (GO–CO2H) have been found to efficiently promote the heterogeneous and environmentally friendly pinacol rearrangement of 1,2-diols and the direct nucleophilic substitution of allylic alcohols. In general, high yields and regioselectivities are obtained in both reactions using 20 wt % of catalyst loading and mild reaction conditions.
Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand
Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
supporting information, p. 10132 - 10135 (2016/08/31)
Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.
Metalloporphyrinic framework containing multiple pores for highly efficient and selective epoxidation
Yang, Xiu-Li,Wu, Chuan-De
supporting information, p. 4797 - 4799 (2014/06/09)
Metalloporphyrin MnIIICl-5,10,15,20-tetrakis(3,5- biscarboxylphenyl)porphyrin, having eight carboxylate groups in multiple coordination modes, connects with paddle-wheel Zn2(COO)4 units for the construction of an interesting porous porphyrinic framework that demonstrates high efficiency and stability upon epoxidation of olefins with excellent substrate size selectivity.
Four metalloporphyrinic frameworks as heterogeneous catalysts for selective oxidation and aldol reaction
Zou, Chao,Zhang, Tianfu,Xie, Ming-Hua,Yan, Lijun,Kong, Guo-Qiang,Yang, Xiu-Li,Ma, An,Wu, Chuan-De
, p. 3620 - 3626 (2013/05/09)
Four porous metalloporphyrinic framework materials, [(CH3) 2NH2][Zn2(HCOO)2(Mn III-TCPP)]·5DMF·2H2O (1; H6TCPP = tetrakis(4-carboxyphenyl)porphyrin), [(CH3)2NH 2][Cd2(HCOO)2(MnIII-TCPP)] ·5DMF·3H2O (2), [Zn2(HCOO)(Fe III(H2O)-TCPP)]·3DMF·H2O (3), and [Cd3(H2O)6(μ2-O)(Fe III-HTCPP)2]·5DMF (4) were synthesized by heating a mixture of MIIICl-H4TCPP (M = Mn and Fe) and M′ (M′ = Zn or Cd) nitrate in a mixed solvent of DMF and acetic acid. Compounds 1-3 are built up from M′2(COO)4 paddle-wheel subunits bridged by MIII-TCPP and formate ligands to form their 3D connections. The formate pillar heterogeneously connects with M and M′ cations in 1 and 2 and homogeneously joins M′ cations in 3. The μ2-O bridged FeIII-HTCPP dimer performs as a decadentate ligand to link 10 cadmium cations for the formation of an interesting 3D coordination network of 4. The four porphyrinic frameworks present interesting catalytic properties in the selective epoxidation of olefins, oxidation of cyclohexane, and intermolecular aldol reaction of aldehydes and ketones.
Highly efficient C-H oxidative activation by a porous Mn III-porphyrin metal-organic framework under mild conditions
Xie, Ming-Hua,Yang, Xiu-Li,He, Yabing,Zhang, Jian,Chen, Banglin,Wu, Chuan-De
, p. 14316 - 14321 (2013/11/06)
A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed-metal-organic framework (M'MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M'MOF of [Zn2(MnOH-TCPP)- (DPNI)]·0.5DMF·EtOH·5.5H2O (CZJ-1; CZJ = Chemistry Department of Zhejiang University; TCPP = tetra-kis(4-carboxyphenyl) porphyrin); DPNI = N, N′-di(4-pyridyl)-1, 4, 5, 8-naph- thalenetetracarboxydiimide) has the type of doubly interpenetrated cubic aPo topology in which the basic Zn2-(COO)4 paddle-wheel clusters are bridged by metalloporphyrin to form two-dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three-dimensional porous structure. The porosity of CZJ-1 has been established by both crystal-lographic studies and gas-sorption isotherms. CZJ-1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94% to the mixture of cyclohexanone (K) and cyclohexanol (A) (so-called K-A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M'MOF catalyst.
Lewis acid-promoted electron transfer deoxygenation of epoxides, sulfoxides, and amine N-oxides: the role of low-valent niobium complexes from NbCl5 and Zn
Oh, Kyungsoo,Knabe, William Eric
supporting information; experimental part, p. 2966 - 2974 (2009/05/30)
A mild and operationally simple deoxygenation of epoxides, sulfoxides, and amine N-oxides is described using a sub-stoichiometric amount of low-valent niobium complexes generated in situ from commercially available NbCl5 and zinc dust. The deoxygenation proceeds by a reductive cleavage of polarized O-C/O-N/O-S bonds through a single electron transfer from zinc metal to the niobium-substrate complex due to the high oxophilic nature of the niobium species. The presence of adjacent radical-stabilizing groups is beneficial to epoxide substrates; however the similar prerequisite does not apply to sulfoxides and amine N-oxides, where a broad range of substrates are efficiently deoxygenated in excellent yields.
o-benzenedisulfonimide as reusable bronsted acid catalyst for acid-catalyzed organic reactions
Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano,Venturello, Paolo
, p. 1379 - 1388 (2008/12/21)
Acid-catalyzed organic reactions, such as etherification, esterification, acetal synthesis, cleavage, and interconversion, and pinacol rearrangement were carried out in the presence of catalytic amounts of o-benzenedisulfonimide as Bronsted acid catalyst; the conditions were mild and selective. The catalyst was easily recovered and purified, ready to be used in further reactions, with economic and ecological advantages. Georg Thieme Verlag Stuttgart.
