Catalytic asymmetric transfer hydrogenation of ketones: recent advances

In this review, we consider the main processes for the asymmetric transfer hydrogenation of ketones from 2008 up today. The most effective organometallic compounds (derived from Ru, Rh, Ir, Fe, Os, Ni, Co, and Re) and chiral ligands (derived from amino alcohols, diamines, sulfur- and phosphorus-containing compounds, as well as heterocyclic systems) will be shown paying special attention to functionalized substrates, tandem reactions, processes under non-conventional conditions, supported catalysts, dynamic kinetic resolutions, the use of water as a green solvent, theoretical and experimental studies on reaction mechanisms, enzymatic processes, and finally applications to the total synthesis of biologically active organic molecules.

Catalytic Asymmetric Transfer Hydrogenation of Imines: Recent Advances

In this review article recent developments in the asymmetric transfer hydrogenation of imines from 2008 up to today are presented. The main methodology involves either metal-catalyzed procedures in the presence of a chiral ligand or organocatalyzed technologies using a Hantzsch ester and a chiral BINOL-derived phosphoric acid. The most important procedures are collected, paying special attention to the application of this methodology in synthetic organic chemistry.

Micromechanical modelling of bending under tension forming behaviour of dual phase steel 600

A micromechanical modelling based approach by means of a Representative Volume Element (RVE) was employed to predict the flow behaviour and plastic strain of DP600 steel, produced by WISCO. Macroscopic modelling of a classical Bending-Under-Tension (BUT) experiment was employed to acquire strain deformation, and thus the following microscopic modelling was implemented by considering the realistic microstructure morphology. Comparisons between macroscopic behaviour and microscopic behaviour, including strain distribution and stress distribution, were extracted for different boundary conditions of the BUT set-up. The micro-macro modelling approach increases the understanding of the steel microstructure, which will enable this microstructure to be tailored for different applications in automobile industry in the future.

Modeling the effect of asymmetric rolling on mechanical properties of Al-Mg alloys

The mechanical behavior under uniaxial tension of Al-Mg alloy 5182 pre-deformed in conventional rolling (CR), asymmetric rolling-continuous (ASRC), and asymmetric rolling-reversed (ASRR) was investigated and modeled with a rate dependent crystal plasticity finite element method and VPSC (Visco-Plastic Self Consistent) model. M-K theory combined with Yld2000 model by Barlat et al. (Int. J. Plasticity 2003, 19, 1297) was used to predict the strain-based and stress-based formability for AA 5182 material. It was concluded that the new ASRR process has very compatible formability with improved strength compared to CR process. These merits can be directly applied for clam-shell resistant design in rigid-packaging industry.

Symmetric and asymmetric rolling of low carbon steels

 In this study, it is shown that a close to ideal shear texture can be formed throughout the thickness of a rolled sheet. Such rotation of rolling texture not only leads to the enhancement in grain refinement but also the secondary processing as compared to the symmetric rolling.

Analysis of texture and R value variations in asymmetric rolling of if steel

Asymmetric rolling (ASR) is a potential process to reach better grain refinement than in conventional rolling, thus, can lead to better mechanical properties. It is not known, however, how the introduction of a shear component will change the ideal orientations of the textures, and consequently, the evolution of plastic anisotropy. To understand the effect of the added shear on texture evolution in ASR, a stability analysis is carried out in orientation space and the variations in the position and strength of the ideal orientations are analysed as a function of the shear component. Then, modelling of R values is presented for various cases. On that basis, it is shown that there is an upper limit for the shear component in asymmetric rolling that still retains the 〈1 1 1〉 ND fibre (ND: direction normal to the sheet) which is good for formability. It is also found that better persistence of the ND fibre can be obtained by cyclically alternating the shear component. The theoretical results are well supported by comparison to experimental evidences. © 2011 Elsevier B.V. All rights reserved.

Asymmetric accumulative roll bonding of aluminium-titanium composite sheets

Aluminium-titanium (Al/Ti) composite sheets were fabricated via asymmetric accumulative roll bonding (AARB), which capitalises on additional shear to enhance plastic deformation. Multi-layers of Al alloy (AA1050) and commercially-pure Ti sheets were alternatively stacked and rolled-bonded with varied roll diameter ratios (dr) ranging from 1 to 2, for up to four passes. Annealing of selected composite sheets was subsequently carried out at 600°C for 24h to compare the rates of solid-state diffusion reactions between Al and Ti components. Mechanical tests revealed that both tensile strength and ductility of the sheets increase systematically with dr. The microstructures and the Al/Ti interfaces of the sheets were analysed in detail using TEM, SEM and FIB techniques. It is shown that not only does AARB lead to a more refined grain size of the Al matrix but also it promotes the development of a nanostructured surface layer on Ti that comprises crystallites of 50-100nm in size, which is otherwise absent in the case of symmetric ARB (i.e. dr=1). The AARB-processed sheets exhibit a larger thickness of the interdiffusion layer at the Al/Ti interfaces than the counterparts processed via the symmetric ARB route, the difference being in excess of 15%. The effects and the implications of AARB processing on mechanical behaviour and diffusion kinetics are discussed with respect to the microstructural evolutions.

Improvement of accuracy in a free bending test for material characterization

The effect of secondary (anticlastic) curvature and the stress state on the measurement of material properties in a free bending test is studied in order to improve the accuracy of the test. Experiments and numerical analysis are conducted on a medium strength 304L stainless steel and high strength dual-phase steels, DP780 and DP1000. The dependence of the secondary curvature on sample geometry is analysed and correction factors are introduced to improve the accuracy of the calculation of material properties when using plane strain or uniaxial stress two-dimensional assumptions. A free bending test procedure is proposed to characterize material behaviour close to yield. This will allow the quick and simple analysis of material properties for bending-dominated forming processes such as roll forming.

Microstructure and texture evolution during symmetric and asymmetric rolling of a martensitic Ti-6Al-4V alloy

In the current study, the effect of deformation mode (i.e., symmetric vs asymmetric rolling) on the extent of grain refinement and texture development in Ti-6Al-4V was examined through warm rolling of a martensitic starting microstructure. During rolling, the initial martensitic lath structure was progressively fragmented, primarily through continuous dynamic recrystallization. This eventually led to an ultrafine-grained (UFG) microstructure composed of equiaxed grains with a mean size of 180 to 230 nm, mostly surrounded by high-angle grain boundaries. Depending on the rolling reduction and deformation mode (symmetric and asymmetric), the rolled specimens displayed different layer morphologies throughout the specimen thickness: a fully UFG surface layer, a partial UFG transition layer, and a partially fragmented lath interior layer. Due to a higher level of effective strain and continuous rotation of the principle axis, asymmetric rolling resulted in a greater extent of grain refinement compared with symmetric rolling at a given thermomechanical condition. A bulk UFG structure was successfully obtained using 70 pct asymmetric rolling. In addition, the rolling texture exhibited various characteristics throughout the thickness due to a different combination of shear and compressive strains. Principally, the basal texture component was displaced from the normal toward rolling direction during asymmetric rolling, differing from the symmetric rolling textures.

Bending fatigue testing of commercial purity titanium for dental implants

High fatigue strength is one of the major requirements for dental implant materials. It was previously shown that the fatigue strength under conventional stress-control tension–compression testing can be doubled for commercially pure (CP) titanium processed by equal channel angular pressing. However, the fatigue endurance of an implant exposed to cyclic loading in corrosive media (bodily fluids) may potentially be compromised. In this work, non-conventional bending fatigue testing in air and in simulated body fluid (SBF) has been carried out for coarse-grained and ultrafine-grained CP titanium.

Finding line of action of the force exerted on erect spine based on lateral bending test in personalization of scoliotic spine models

In multi-body models of scoliotic spine, personalization of mechanical properties of joints significantly improves reconstruction of the spine shape. In personalization methods based on lateral bending test, simulation of bending positions is an essential step. To simulate, a force is exerted on the spine model in the erect position. The line of action of the force affects the moment of the force about the joints and thus, if not correctly identified, causes over/underestimation of mechanical properties. Therefore, we aimed to identify the line of action, which has got little attention in previous studies. An in-depth analysis was performed on the scoliotic spine movement from the erect to four spine positions in the frontal plane by using pre-operative X-rays of 18 adolescent idiopathic scoliosis (AIS) patients. To study the movement, the spine curvature was considered as a 2D chain of micro-scale motion segments (MMSs) comprising rigid links and 1-degree-of-freedom (DOF) rotary joints. It was found that two MMSs representing the inflection points of the erect spine had almost no rotation (0.0028° ± 0.0021°) in the movement. The small rotation can be justified by weak moment of the force about these MMSs due to very small moment arm. Therefore, in the frontal plane, the line of action of the force to simulate the left/right bending position was defined as the line that passes through these MMSs in the left/right bending position. Through personalization of a 3D spine model for our patients, we demonstrated that our line of action could result in good estimates of the spine shape in the bending positions and other positions not included in the personalization, supporting our proposed line of action.

Explaining commodity prices through asymmetric oil shocks: evidence from nonlinear models

Linkages between oil and 25 other commodity prices are examined using annual data for 1900 to 2011. We identify long-run relationships using both linear and nonlinear ARDL models and capture short-run causalities through asymmetric Granger causality tests. Nonlinearity can't be rejected for the relationship between oil and most other commodity prices. Long-run positive impacts of oil price increases are found for 20 commodities and short-run negative impacts for 13 commodity prices. Oil prices don't have much impact on beverage or cereal prices once endogeneity is accounted for, but they have substantial impact on metal prices.

Asymmetric Syntheses of Analogs of Kainic Acid

Kainic acid has been used for nearly 50 years as a tool in neuroscience due to its pronounced neuroexcitatory properties. However, the significant price increase of kainic acid resulting from the disruption in the supply from its natural source, the alga Digenea Simplex, as well as inefficient synthesis of kainic acid, call for the exploration of functional mimics of kainic acid that can be synthesized in a simpler way. Aza kainoids analog could be one of them. The unsubstituted aza analog of kainoids has demonstrates its ability as an ionotropic glutamate receptor agonist and showed affinity in the chloride dependent glutamate (GluCl) binding site. This opened a question of the importance of the presence of one nitrogen or both nitrogens in the aza kainoid analogs for binding to glutamate receptors. Therefore, two different pyrrolidine analogs of kainic acid, trans-4-(carboxymethyl)pyrrolidine-3-carboxylic acid and trans-2-carboxy-3-pyrrolidineacetic acid, were synthesized through multi-step sequences. The lack of the affinity of both pyrrolidine analogs in GluCl binding site indicated that both nitrogens in aza kainoid analogs are involved in hydrogen bonding with receptors, significantly enhancing their affinity in GluCl binding site. Another potential functional mimic of kainic acid is isoxazolidine analogs of kainoids whose skeleton can be constituted directly via a 1, 3 dipolar cycloaddition as the key step. The difficulty in synthesizing N-unsubstituted isoxazolidines when applying such common protecting groups as alkyl, phenyl and benzyl groups, and the requirement of a desired enantioselectivity due to the three chiral ceneters in kainic acid, pose great challenges. Hence, several different protected nitrones were studied to establish that diphenylmethine nitrone may be a good candidate as the dipole in that the generated isoxazolidines can be deprotected in mild conditions with high yields. Our investigations also indicated that the exo/endo selectivity of the 1, 3 dipolar cycloaddition can be controlled by Lewis acids, and that the application of a directing group in dipolarophiles can accomplish a satisfied enantioselectivity. Those results demonstrated the synthesis of isoxazoldines analogs of kainic acid is very promising.

Exploring the scope of asymmetric synthesis of β-Hydroxy-γ-lactams via Noyori-type reductions

Enantio- and diastereoselective hydrogenation of β-keto-γ-lactams with a ruthenium–BINAP catalyst, involving dynamic kinetic resolution, has been employed to provide a general, asymmetric approach to β-hydroxy-γ-lactams, a structural motif common to several bioactive compounds. Full conversion to the desired β-hydroxy-γ-lactams was achieved with high diastereoselectivity (up to >98% de) by addition of catalytic HCl and LiCl, while β-branching of the ketone substituent demonstrated a pronounced effect on the modest to excellent enantioselectivity (up to 97% ee) obtained.