Radical Reactions and Its Synthetic Application

1 Introduction Strategies involving radical reactions have become preeminent tools in organic synthesis. Free radical-mediated cyclization has developed as a powerful method for preparing various types of cyclic compounds via carbon-carbon bond-forming processes. In order to develop effective and convenient methods for the synthesis of biologically active cyclic amines, we have focused our efforts on radical reactions using aldehydes, ketones, and C-C multiple bonds as a radical precursor and…     

New Approach to the Synthesis of C-Glycosides

C-glycosides are important carbohydrate mimetics and have gained considerable attention because ot their attractive biological activities as pharmaceutical targets and their resistance to enzymatic degradation in vivo. Consequently, a large number of C-glycosides have been synthesized for their bioactivity investigation, and various synthetic methodologies have been developed. As a continuation of the synthesis of novel C-glycoside derivatives using exo-glycals as the precursor, we wish to present herein new approaches to the synthesis of C-aryl aminoglycoside via the 1,3-dipolar cycloaddition （Scheme 1 ） and C-disaccharides by Suzuki cross-coupling reaction （Scheme 2）, and the synthesis of dihydropyrimidinonyl （DHPM） glycoside by the three component Biginelli reaction （Scheme 3）.     

Dipiphosphinoazines-from Rich Coordination Variability to Catalysis

1 Results Diphosphinoazines are very versatile,potentially up to tetradentate ligands,known to form complexes with many transition metals.Recently,we developed synthesis of diphosphinoazines with various substituents on phosphorus donor atoms.This fine tuning allowed to design novel catalytic systems for several organic reactions.Hydroamination of Michael-type substrates with selected primary and secondary amines revealed the reactivity of some amines in non-catalyzed reaction.Hydroamination of methyl methacrylate by morpholine was catalyzed by palladium cationic complexes of type 1[1]. Cationic nickel complexes of type 2 are,in combinations with usual activators like MAO,catalysts for ethylene polymerization[2]. Palladium complexes with diphosphinoazine backbone in a deprotonated pincer-like form (type 3) are efficient catalysts for the Mizoroki-Heck reaction of bromoarenes and activated chloroarenes[3].See Fig.1.     

Double Nucleophilic Addition of Ketene Silyl (THIO)Acetals and Trimethylsilyl Cyanide to N-Allylideneamine

1 Results We have already published a double nucleophilic addition reaction of α,β-unsaturated imines with several nucleophiles such as ketene silyl acetals, trimethylsilyl cyanides, trimethylsilyl azides and thiols[1]. However, it was not easy to use N-allylideneamine 2 derived from acrolein for such reactions. Since there is no substituent at the β-position, imine 2 has high reactivity and are prone to be polymerization. We report the first synthesis of N-allylideneamines 2 using the isomerization of propargylamines 1 having N-trityl and diphenylethyl groups. We also found that ketene silyl acetals and ketene silyl thioacetals underwent 1,4-and 1,2-addition reaction with N-allylideneamine 2 to give the desired double nucleophilic addition products in high yields. Moreover, amino nitriles 3 were obtained in good yields after work-up with TFA.See scheme 1.     

Highly Efficient Asymmetric Synthesis Usomg Organocatalyst Derived From(S)-proline

1 Results Much effort has been focused on organocatalytic asymmetric synthesis in these several years. We have already documented highly efficient organocatalytic asymmetric acylation of a wide variety of racemic alcohols and meso-diols catalyzed bya chiral 1,2-diamine derived from (S)-proline[1]. (S)-Homoproline seems to be a potentially interesting organocatalyst, but no examples using (S)-homoproline itself in asymmetric synthesis has been reported. We have accomplished an efficient and practical synthesis of (S)-homoproline, which is a one-carbon homologated proline, starting from (S)-proline in 7 steps. And then we have developed a novel asymmetric Michael additionreaction of ketones to β-nitrostyrene and its derivatives using (S)-homoproline as a chiral organocatalyst. The reaction was performed in a highly diastereoselective and enantioselective manner over 90% ee[2].     

Iron-catalyzed one-pot reactions of o-aryloxybenzaldehydes to xanthones

An efficient one-pot procedure for the synthesis of multisubstituted xanthone derivatives using Fe-catalyzed reactions of 2-aryloxybenzaldehydes followed by DDQ(2,3-dichloro-5,6-dicyano-1,4-benzoquinone) oxidation has been developed.This method offers a convenient high-yield route to xanthones from easily accessible starting materials.     

Recent advances in the iron-catalyzed cycloaddition reactions

The rapid generation of molecular in a relatively easy manner has made the cycloaddition reaction a powerful tool in the synthesis of different membered ring compounds.Clearly,iron catalysts are becoming a much more interesting and viable choice for this purpose.In this review,a number of promising results in the iron catalyzed cycloaddition reactions in the last decades were summarized.Special attention has been paid to the asymmetric cycloaddition reactions.     

Double Nucleophilic Addition of Ketene Silyl (THIO)Acetals and Trimethylsilyl Cyanide to N-Allylideneamine

1 Results We have already published a double nucleophilic addition reaction of α,β-unsaturated imines with several nucleophiles such as ketene silyl acetals, trimethylsilyl cyanides, trimethylsilyl azides and thiols[1]. However, it was not easy to use N-allylideneamine 2 derived from acrolein for such reactions. Since there is no substituent at the β-position, imine 2 has high reactivity and are prone to be polymerization. We report the first synthesis of N-allylideneamines 2 using the isomerization of ...     

Synchrotron X-ray diffraction techniques for in situ measurement of hydride formation under several gigapascals of hydrogen pressure

The high-pressure technique is a fundamental tool for realizing novel phase transitions, chemical reactions, and other exotic phenomena. Hydrogenation is one example of a high-pressure reaction; at high pressures of several gigapascals, hydrogen becomes chemically active and reacts with metals and alloys to form hydrides. This paper covers a high-pressure study of the hydrogenation process and the synthesis of hydrides using a cubic-type multi-anvil apparatus. The experimental details of a hydrogenation cell assembly, high-temperature and highpressure generation, and an in situ observation technique are presented. These experiments are conducted with the aid of in situ synchrotron radiation X-ray diffraction measurements operated in an energy-dispersive mode in the conventional manner for time-resolved measurements and a newly developed angle-dispersive mode for observation of the crystal growth process during formation of metal hydrides. Two successful cases of high-pressure hydrogenation are presented： aluminum hydride, Al H3, and an aluminum-based alloy hydride, Al2 Cu Hx, which are potential candidates for hydrogen storage materials.     

Electron transfer in N-butylpyridinium tetrafluoroborate ionic liquid by pulse radiolysis

The radiolysis behavior of neat pyridinium ionic liquids (ILs) and their aqueous solutions was investigated using nanosecond pulse radiolysis techniques. Radiolysis of the ionic liquids, such as N-butylpyridinium tetrafluoroborate (BuPyBF4 ), resulted in the formation of solvated electrons and organic radicals. Solvated electrons reacted with the pyridinium moiety to produce a pyridinyl radical, which can transfer electrons to various acceptors. The electron-transfer rate constants of the solvent-derived butylpyridinyl radicals in BuPyBF 4 and in several compounds (for example, duroquinone, 4,4′-pyridine, benzophenone, and 1,1′- dimethyl-4,4′-bypyridinium dichloride) (k of the order 10 8 L/(mol s) were lower than those measured in water and in i-PrOH but were significantly higher than the diffusion-controlled rate constants estimated based on viscosity. The electron-transfer rate constants in neat BuPyBF 4 were one order of magnitude faster than the diffusion-controlled values. This finding suggests that Bu- PyBF 4 acts not only as solvent but also as active solute, such as in solvent-mediated reactions. These reactions result in electrons reaching their final destinations via intervening pyridinium groups without requiring the diffusion of a specific radical.     

The Mechanism of Cumene Peroxidation Catalyzed by Cobalt(Ⅱ)-Chelated Copolymer

1Introduction The functionalised polymers, especially for chelating polymer, have been employed to considerable effects in organic synthesis for several decades. The use of polymer groups as ligands permits the ligand surroundings to be varied and regulation of the catalytic properties of the complexes because of the flexibility of the polymer chains, their ability to adopt various conformations, and the possibility of creating various spatial distributions of metal centers immobilized on the polymer chains[1,2]. In our recently studies[3-5], the chelating copolymer with imino-diacetic acid chelating group in the polymer side chain was manufactured, and which can increase effectively amount of the chelating group within the polymer. Meanwhile, the high catalysis performance in organic synthesis had also been proved via benzaldehyde and cumene peroxidation. For cumene peroxidation,it is hardly to find such a simple catalyst with high conversion and selectivity due to hydroperoxide decomposition by a radical mechanism. The cumene peroxidation by catalyst system and its reaction mechanism as well as the kinetic study are popularly investigated object for many researchers[6-9]. However, the reaction mechanism still does not clear owing to the by-products will be produced following the different catalysts used.     

A comparison of transition state of phenol in H-atom abstraction by methyl and methylperoxyl radicals

DFT method was employed to locate transition state for H-atom transfer from phenol by methyl radical and methylperoxyl radical. The reaction pathway energy profiles and the structure of transition state show that a common feature is the out-of-plane structure of the transition state: in contrast to the en- ergetic minima of a hydrogen-bonded intermediate, the hydrogen bond in transition structures is con- siderably twisted out of the aromatic ring. From the values of enthalpy (△H) and activation energy (Ea) obtained, it is found that the rate of the reaction of peroxyl radical with phenolic antioxidant is higher than that of alkyl radical with antioxidant. Spin density distributions show that the electron transmis- sion is between methyl (methylperoxyl) radical and phenol.     

Synthesis of Novel Fuctionalized Glycosides Based on 1,3-Dipolar Cycloaddition

1 Results 1,3-Dipolar cycloaddition reaction is one of the most common methods for preparing various five membered heterocycles,and provides a conveniet protocols for constructing C-C bond with functional groups.The reaction has also been successfully used in the syntheses of C-glycosides and other sacharride derivatives.We wish to present herein our recent approaches on the synthesis of novel C-amino-glycosides,C-aminodisaccharides,spiro heterocyclic glycosides and heterocycle linked C-disaccharides,etc.via the 1,3-dipolar cycloaddition of carbohydrate oleffins to nitrones and nitrile oxides (Scheme 1).The cycloadditions of exo-glycals (1) and the C-glycosyl oleffin (7) Scheme 1 with the nitrones and nitrile oxides were carried out by refluxing a toluene solution and provided the corresponding intermediates of glycosyl isoxazolidines (2) and glycosyl isoxazolines (5) and (8),followed by a series reactions of reduction,deprotection,etc.to afford the novel functionalized C-glycosides (3),(4),(6) and (9).     

Microstructure evolution of laser rapidly solidified Al-Mn alloys

A series of laser surface remelting experiments of Al-1.1, 3.2 and 5.6 wt% Mn alloys has been conducted using a 5 kW CW CO2 laser, and the microstructures of samples have also been investigated. The experimental results show that no apparent eutectic growth appears in the whole growth rate range for Al-3.2 wt% Mn alloy under laser rapid solidification condition, and the microstructure grows in the form of α(Al) cell/dendrite. With the increase of growth rate, the microstructures of Al-5.6wt%Mn alloy change from Al6Mn dendrite to α(Al) +Al6Mn eutectic, α(Al) cellular/dendrite and segregation-free solid solution. The critical rates of Al-1.1, 3.2 and 5.6 wt% Mn alloys to attain absolute stability are 44.1, 134.6 and 230.1 mm/s respectively, and a reasonable agreement has been found between the experimental results and those calculated according to Mullins-Sekerka's theory.     

Titanium Iodies Mediated Intriguing Transformation of Organic Molecules

1 Results Titanium iodides have been found to be good reagents for iodination,reductive formation of enolates,pinacol coupling,and so on.Following new reactions will be discussed:(1) Iodination: Titanium(Ⅳ) iodide is a good iodination reagent for olefins and acetylenes.Simple olefins are iodotitanated with titanium (Ⅳ) iodide to give,after quenching with water,iodoalkanes in moderate to good yields.Phenylacetylene gives α-iodostyrene,whereas 2,2-diiodoalkanes are major products from 1-alkynes when they are treated with titanium (Ⅳ) iodide.In the presence of acetals,the reaction gives intriguing C-C bond forming products.     

Functional Materials for Catalytic and Magnetic Applications

1 Introduction Metal, metal oxide and metal compound nanoparticles (NPs) received considerable attention due to their unique properties: catalytic, magnetic, optical, electronic, etc. We believe that for different applications, there are preferable morphologies of NP-stabilizing medium composites. For example, small (1-3 nm) nanoparticles formed in micro/mesoporous hypercrosslinked polystyrene demonstrate excellent catalytic properties in various hydrogenation and oxidation reactions due to high surface area and availability of catalytic centers for reacting molecules. On the other hand, a similar morphology of magnetic metal oxide nanoparticles yields only mediocre magnetic properties because the polymeric matrix used for nanoparticle growth and stabilization limits the choice of the reaction conditions of the NP synthesis.     

Synthesis of zeolite membranes

Zeolite membranes offer great application potentials in membrane separation and/or reaction due to their excellent separation performance and catalytic ability. Up to present, various synthesis methods of zeolite membranes have been developed, including embedded method, in-situ hydrothermal synthesis method, and secondary growth method etc. Compared with the in-situ hydrothermal synthesis method, the secondary growth method possesses a variety of advantages such as easier operation, higher controllability in crystal orientation, microstructure and film thickness,leading to much better reproducibility. This review provides a concise summary and analysis of various synthesis methods reported in the literature. In particular, the secondary growth method was discussed in detail in terms of crystal orientation, defects and crystal grain layers. Some critical issues were also highlighted, which were conducive to the improvement in the synthesis technology of zeolite membranes.     

Unexpected and Intriguing Reactivity of Imino Compounds

We have recently discovered a tandem N-alkylation-C-allylation reaction of α-imino esters with organoaluminum reagents and allyltributyltin. In this reaction, iminium salts were readily prepared in situ by the oxidation of aluminum enolates, and the subsequent nucleophilic addition proceeded smoothly to afford N-alkylation-C-allylation products in good yields. During these studies, we focused on the generation of iminium species 2 by oxidizing a readily accessible and stable enol derivative with oxidants. A convenient method has been found for the generation of α-alkoxycarbonyl iminium salts 2 from ketene silyl acetals and the subsequent reaction with nucleophiles.     

Russian Nuclear Rocket Engine Design for Mars Exploration

This paper is to promote investigation into the nuclear rocket engine (NRE) propulsion option that is considered as a key technology for manned Mars exploration. Russian NRE developed since the 1950s in the former Soviet Union to a full-cale prototype by the 1990s is viewed as advantageous and the most suit-able starting point concept for manned Mars mission application study. The main features of Russian het-erogeneous core NRE design are described and the most valuable experimental performance results are summarized. These results have demonstrated the significant specific impulse performance advantage of the NRE over conventional liquid rocket engine (LRE) propulsion technologies. Based on past experience, the recent developments in the field of high-temperature nuclear fuels, and the latest conceptual studies, the developed NRE concept is suggested to be upgraded to the nuclear power and propulsion system (NPPS), more suitable for future manned Mars missions. Although the NRE still needs development for space appli-cation, the problems are solvable with additional effort and funding.