Free radical-mediated vinyl amination: access to N,N-dialkyl enamines and their beta-stannyl and beta-thio derivatives

[reaction: see text] The first examples of free radical-mediated vinyl amination are described by nonconventional vinyl radical addition to azomethine nitrogen. This new vinyl amination protocol is mild and provides convenient synthetic access to nonstabilized N,N-dialkyl enamines and tandem bond-forming processes.     

Initiation mechanisms in copolymerization: Reaction of t-butoxyl radicals with co-monomers ethyl vinyl ether and methyl methacrylate

The radical trapping technique employing 1,1,3,3-tetramethyl-1,3-dihydro-1H-isoindol-2-yloxyl as a scavenger has been used to investigate the reaction of t-butoxyl radicals with mixtures of ethyl vinyl ether and methyl methacrylate. The range of identified products includes those from both addition and hydrogen abstraction with both monomers, head addition with ethyl vinyl ether, and some second monomer addition products. Relative rate constants have been obtained for various pairs of constituent reactions. t-Butoxyl radicals add to ethyl vinyl ether one to two times faster than to methyl methacrylate, depending on which monomer is in excess. The ratio is less than 1 in nonolefinic solvents and as high as 6 in t-butanol. This solvent effect is thought to be due to the radicals complexing to either methyl methacrylate or t-butanol (H-bonding), thereby increasing its electrophilic character. © 1997 John Wiley & Sons, Inc.     

Transition-metal free synthesis of diaryl vinyl selenides: a simple synthetic approach with high selectivity

A simple, highly efficient synthetic protocol is developed for the synthesis of unsymmetrical diaryl vinyl selenides from diaryldiselenide and β-bromo styrene under transition-metal free conditions in N,N′-dimethyl propylene urea and 130 °C to afford high yields and excellent selectivities. This method provides a new strategy to fabricate a wide variety of important substituted molecular skeletons and an alternative to conventionally used metal salts, additives, and ligands.     

Titanocene-catalysed, selective reduction of ketones in aqueous media. A safe, mild, inexpensive procedure for the synthesis of secondary alcohols via radical chemistry

We report here a novel procedure for the reduction of ketones to secondary alcohols using catalytic quantities of commercially available Cp₂TiCl₂, inexpensive Zn dust and water as proton source. Mechanistically the reaction presumably proceeds via titanoxy radicals. In practice this reduction process has significant advantages: it shows an interesting selectivity pattern, takes place under mild conditions using safe, cheap reagents and does not require anhydrous solvents. The proton-donor activity of water under these conditions avoids the use of the frequently poisonous hydrogen-atom donors generally required to reduce free radicals. This procedure is also highly convenient for synthesising deuterium-labelled alcohols employing relatively inexpensive D₂O as deuterium source.     

Stereo- and regiospecific cu-catalyzed cross-coupling reaction of vinyl iodides and thiols: a very mild and general route for the synthesis of vinyl sulfides

A mild and efficient method for the copper-catalyzed formation of vinylic carbon-sulfur bonds has been developed. The desired vinyl sulfides are obtained in good to excellent yields, with full retention of stereochemistry. This method is particularly noteworthy given its mild reaction conditions, simplicity, and generality, as well as low cost of the catalyst system.     

超分子自由基:构筑、调控与功能

自由基既是新型功能材料的构筑基元,也是常见的反应中间体.调控自由基的活性,具有重要的理论意义和应用价值.为此,我们提出了"超分子自由基"的概念,系指通过非共价作用稳定或活化的自由基.基于葫芦脲的主客体化学,构筑了不同结构的超分子自由基,借助葫芦脲分子的结构特征,从三个方面对自由基的活性进行调控：（1）利用葫芦脲的空间位阻效应和静电效应,稳定自由基阴离子,从而构筑了新型有机近红外光热转换材料,并应用于选择性抗菌;（2）利用葫芦脲的静电效应,活化自由基阳离子,实现了对芬顿氧化反应的显著加速;（3）利用葫芦脲主客体化学的动态可逆性,实现了对反应中间体活性的自适应调控,从而显著地提升了醇氧化反应的催化效率.上述研究表明,构筑简便、活性可调的超分子自由基在功能材料和超分子催化领域具有广阔的应用潜力,未来有望得到进一步的发展.     

Free Radicals as a Double-Edged Sword: The Cancer Preventive and Therapeutic Roles of Curcumin

Free radicals, generally composed of reactive oxygen species (ROS) and reactive nitrogen species (RNS), are generated in the body by various endogenous and exogenous systems. The overproduction of free radicals is known to cause several chronic diseases including cancer. However, increased production of free radicals by chemotherapeutic drugs is also associated with apoptosis in cancer cells, indicating the dual nature of free radicals. Among various natural compounds, curcumin manifests as an antioxidant in normal cells that helps in the prevention of carcinogenesis. It also acts as a prooxidant in cancer cells and is associated with inducing apoptosis. Curcumin quenches free radicals, induces antioxidant enzymes (catalase, superoxide dismutase, glutathione peroxidase), and upregulates antioxidative protein markers–Nrf2 and HO-1 that lead to the suppression of cellular oxidative stress. In cancer cells, curcumin aggressively increases ROS that results in DNA damage and subsequently cancer cell death. It also sensitizes drug-resistant cancer cells and increases the anticancer effects of chemotherapeutic drugs. Thus, curcumin shows beneficial effects in prevention, treatment and chemosensitization of cancer cells. In this review, we will discuss the dual role of free radicals as well as the chemopreventive and chemotherapeutic effects of curcumin and its analogues against cancer.     

Bis[bis-(4-alkoxyphenyl)amino] derivatives of dithienylethene, bithiophene, dithienothiophene and dithienopyrrole: palladium-catalysed synthesis and highly delocalised radical cations

Five diamines with thiophene-based bridges--(E)-1,2-bis{5-[bis(4-butoxyphenyl)amino]-2-thienyl}ethylene (1), 5,5'-bis[bis(4-methoxyphenyl)amino]-2,2'-bithiophene (2), 2,6-bis[bis(4-butoxyphenyl)amino]dithieno[3,2-b:2',3'-d]thiophene (3), N-(4-tert-butylphenyl)-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 a) and N-tert-butyl-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 b)--have been synthesised. The syntheses make use of the palladium(0)-catalysed coupling of brominated thiophene species with diarylamines, in some cases accelerated by microwave irradiation. The molecules all undergo facile oxidation, 4 b being the most readily oxidised at about -0.4 V versus ferrocenium/ferrocene, and solutions of the corresponding radical cations were generated by addition of tris(4-bromophenyl)aminium hexachloroantimonate to the neutral species. The near-IR spectra of the radical cations show absorptions characteristic of symmetrical delocalised species (that is, class III mixed-valence species); analysis of these absorptions in the framework of Hush theory indicates strong coupling between the two amine redox centres, stronger than that observed in species with phenylene-based bridging groups of comparable length. The strong coupling can be attributed to high-lying orbitals of the thiophene-based bridging units. ESR spectroscopy indicates that the coupling constant to the amino nitrogen atoms is somewhat reduced relative to that in a stilbene-bridged analogue. The neutral species and the corresponding radical cations have been studied with the aid of density functional theory and time-dependent density functional theory. The DFT-calculated ESR parameters are in good agreement with experiment, while calculated spin densities suggest increased bridge character to the oxidation in these species relative to that in comparable species with phenylene-based bridges.     

A SiCl4-ZnCl2 induced general, mild and efficient one-pot, three-component synthesis of β-amido ketone libraries

A general, mild and efficient protocol for the synthesis of β-amido ketone libraries was achieved utilizing tetrachlorosilane and zinc chloride in dichloromethane at ambient temperature via a one-pot, three-component condensation of various aldehydes, ketones and nitriles.     

Chemical and electrochemical grafting of polyaniline onto poly(vinyl chloride): synthesis,characterization, and materials properties

We have designed and developed a new strategy for the chemical and electrochemical graft copolymerization of aniline onto poly(vinyl chloride). For this purpose, first phenylamine groups were incorporated into poly(vinyl chloride) via a nucleophilic substitution reaction in the presence of a solvent composed of 4‐aminophenol, potassium carbonate, and dry N,N‐dimethylformamide at room temperature, in order to avoid cross‐linking. The macromonomer obtained was used in chemical and electrochemical oxidation copolymerization with aniline monomer to yield a poly(vinyl chloride)‐g‐polyaniline (PVC‐g‐PANI) graft copolymer. The chemical structures of samples as representatives were characterized by means of Fourier transform infrared and ¹H nuclear magnetic resonance spectroscopies. The electroactivity behaviors of the synthesized samples were verified under cyclic voltammetric conditions. The electrical conductivity and electroactivity measurements showed that the PVC‐g‐PANI graft copolymer has lower electrical conductivity as well as electroactivity than those of the pure PANI. However, the lower electrical conductivity and electroactivity levels in this material can be improved at the price of solubility and processability. Moreover, the thermal behavior and chemical composition of the synthesized graft copolymer were investigated. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation of a series of novel fluorophores, N-substituted 6-amino and 6,6″-diamino-2,2′:6′,2″-terpyridine by palladium-catalyzed amination

A new series of N-substituted 6-amino- and 6,6″-diamino-2,2′:6′,2″-terpyridine (6-amino- and 6,6″-diamino-tpy) was conveniently synthesized in one-step by Pd-catalyzed amination of bromo-substituted tpys with various amines. For highly coordinating tpy substrates, use of appropriate chelating phosphine ligand was critical to achieve moderate to satisfactory yield. The prepared N-substituted 6-amino- and 6,6″-diamino-tpys exhibited moderate to intense fluorescence in dichloromethane with fine-tuned fluorescence maxima ranging from 385 to 455 nm.     

Metal‐Free Annulation of Arenes with 2‐Aminopyridine Derivatives: The Methyl Group as a Traceless Non‐Chelating Directing Group

A novel annulation reaction between 2‐aminopyridine derivatives and arenes under metal‐free conditions is described. The presented intermolecular transformation provided straightforward access to the important pyrido[1,2‐a]benzimidazole scaffold under mild reaction conditions. The unprecedented application of the methyl group of methylbenzenes as a traceless, non‐chelating, and highly regioselective directing group is reported.     

Practical and general method for the direct synthesis of alkyl fluorides from alcohols under mild conditions: a reinvestigation

Abstract  In contrast to the results presented in a previous report, the direct conversion of alcohols to alkyl fluorides with triphenylphosphine and potassium fluoride in CCl₄/DMF under mild conditions failed. Graphical Abstract        

Four-component couplingvia a sequence of threeAd E reactions involving arenesulfenyl chloride, two alkyl vinyl ether units, and silicon-containing π-donors as a method for the synthesis of polyfunctional compounds

A protocol for the synthesis of polyfunctional compounds by a Lewis acid initiated tandem sequence of threeAd _E reactions of sulfur-containing electrophiles with two alkyl vinyl ether units and silicon containing π-donors is proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 5, pp. 924–932, May, 1998.     

Interactions between free radicals and a graphene fragment: physical versus chemical bonding, charge transfer, and deformation

The adsorption of six free radicals (FRs) respectively on a graphene fragment was studied using a density functional tight‐binding method with the inclusion of an empirical dispersion term in total energy. The results indicate that the different interaction paths between the FRs and the graphene lead to different forms of physical (PA) or chemical adsorptions (CA). The CA appears only in the condition where some of the nonhydrogen atoms are closer to the graphene, with the deformation occurring in the latter. The charge transfer increases with the increase in adsorption energy in every FR‐graphene system. Although the deformation in the graphene is negligible in all PA cases, the FR is closer to the graphene and the graphene deformation is clearer in all CA cases, with all atomic displacements being larger than 0.1 Å. Our findings are useful not only for FR scavenging but also for studying the interaction between general molecules and material surfaces. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Living cationic polymerization of isobutyl vinyl ether using a variety of metal oxides as heterogeneous catalysts: Robust,reusable, and environmentally benign initiating systems

Cationic polymerization of isobutyl vinyl ether (IBVE) was examined using a variety of metal oxides in conjunction with IBVE–HCl adduct as a cationogen in toluene at 0 °C. Iron oxides (α‐Fe₂O₃, γ‐Fe₂O₃, and Fe₃O₄) induced living polymerization in the presence of an added base, ethyl acetate or 1,4‐dioxane, to give polymers with very narrow molecular weight distributions (MWDs). Conversely, with other metal oxides such as Ga₂O₃, In₂O₃, ZnO, Co₃O₄, and Bi₂O₃, polymers with bimodal MWDs, including long‐lived species along with uncontrolled higher molecular weight portions, were produced in the presence of an added base. A small amount of nBu₄NCl or 2,6‐di‐tert‐butylpyridine (DTBP) suppressed the uncontrolled portion to induce controlled reactions with Ga₂O₃, In₂O₃, and ZnO. The roles of these reagents are discussed in terms of the nature of the active sites of the catalyst surface and the polymerization mechanisms. In addition, the reusability of the catalyst, the effect of stirring before and during polymerization, and the estimation of the number of active sites are also described. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 916–926, 2010     

A mild, efficient and environmentally friendly method for the regio- and chemoselective synthesis of enaminones using Bi(TFA)3 as a reusable catalyst in aqueous media

Bismuth(III) trifluoroacetate has been found to be an extremely efficient catalyst for the preparation of β-enaminones in water. In addition, by employing this catalyst, high regio- and chemoselective enamination of carbonyl compounds was achieved.     

Novel photocurable monomers: The synthesis of difunctional vinyl ethers with a phosphonate group and difunctional 1‐propenyl ethers with a phosphonate group and their photoinitiated cationic polymerization

Phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were prepared by the regioselective addition reaction of glycidyl vinyl ether (GVE) or 1‐propenyl glycidyl ether with diaryl phosphonates with quaternary onium salts as catalysts. The reaction of GVE with bis(4‐chlorophenyl) phenylphosphonate gave bis[1‐(4‐chlorophenoxy methyl)‐2‐(vinyloxy)ethyl]phenylphosphonate in a 68% yield. The structures of the resulting phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were confirmed by IR and ¹H NMR spectra and elemental analysis. Photoinitiated cationic polymerizations of the resulting phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were investigated with photoacid generators. The polymerization of vinyl ether groups and 1‐propenyl ether groups of the obtained monomers proceeded very smoothly with a sulfonium‐type cationic photoinitiator, bis[4‐(diphenylsulfonio)phenyl]sulfide‐bis(hexafluorophosphate), upon UV irradiation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3105–3115, 2005