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Highly enantioselective Michael addition of malonates to nitroolefins catalyzed by chiral bifunctional tertiary amine-thioureas based on saccharides

A series of saccharide-derived bifunctional tertiary amine-thioureas for the asymmetric Michael addition reaction have been designed and synthesized. The addition products between malonates and various nitroolefins were obtained in high yields (up to 99%) and excellent enantioselectivities (up to 99% ee). Georg Thieme Verlag Stuttgart.

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Chiral Catalysts,
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Synthesis and characterization of chiral nickel(II) Schiff base complexes and their CD spectra-absolute configuration correlations

Some nickel(II) complexes of quadridentate Schiff bases prepared from the condensation of 2 mol of 2-hydroxyacetophenone (HACP) or dehydroacetic acid (DHA) with 1 mol of optically active propylene-1,2-diamine (pn), trans-cyclohexane-1,2-diamine (chxn) or 1,2-diphenylethylenediamine (dpen) were synthesized and characterized by EA, IR, UV-vis, and CD spectra. The absolute configurations of the three complexes were determined by X-ray single crystal structure measurement and correlated with CD spectroscopy. In this study, special attention is focussed on the CD signals of the related complexes in the d-d transition region, in the hope of obtaining a tentative correlation between the CD pattern and the absolute configuration about the central metal. A new empirical rule for the assignment of the absolute configuration around the nickel ion in each complex and the handedness of the chiral diamine contained in the Schiff base ligand is put forward. In the case of tetra-coordinated pseudo-planar Ni(II) complexes, the rule can be stated as follows: (i) a positive Cotton effect in the d-d region around 550 nm is assigned to the (S)Deltalambda-configuration for the HACP-(S)-pn-Ni, HACP-(SS)-dpen-Ni, DHA-S-pn-Ni, and DHA-(SS)-dpen-Ni derivatives; and (ii) a concomitant inversion of the Cotton effect in the same range is assigned to the (S)Lambdadelta-configuration for the HACP-(SS)-chxn-Ni and DHA-(SS)-chxn-Ni derivatives.

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Chiral Catalysts,
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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1806-29-7, Name is 2,2-Biphenol, molecular formula is C12H10O2. In a Article£¬once mentioned of 1806-29-7, category: chiral-catalyst

Dendrimer-encapsulated Pd nanoparticles as aqueous, room-temperature catalysts for the Stille reaction

We report that dendrimer-encapsulated Pd nanoparticles having a diameter of ?1.7 nm are effective and general catalysts for coupling aryl halides to organostannanes (the Stille reaction) under mild conditions. The significant results of this study are that the Stille reaction is catalyzed by dendrimer-encapsulated Pd nanoparticles in very good yield, in aqueous solution at 23 C, and using only 0.100 atom % of Pd as catalyst.

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Chiral Catalysts,
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MOLECULAR GLASSES WITH FUNCTIONALIZABLE GROUPS

Disclosed herein is a compound having Formula I: or a salt thereof, in which R1, R2 and R3 are as defined herein. Also disclosed are processes to prepare compounds of Formula I and use of compounds of Formula I to prepare stable glassy phases.

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Chiral Catalysts,
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Chiral discrimination of beta-telluride carboxylic acids by NMR spectroscopy

In this work, the nuclei (1H and 125Te) for NMR spectroscopy and enantiopure compounds as chiral solvent agents (CSAs) and chiral derivatisation agents (CDAs) were evaluated under different conditions. The structure of beta-telluride carboxylic acids was also modified to observe the effect on anisochrony.

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Chiral Catalysts,
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Mechanisms of the H2-hydrogenation and transfer hydrogenation of polar bonds catalyzed by ruthenium hydride complexes

The catalytic cycles for the H2-hydrogenation (H) and transfer hydrogenation (T) of C=O and C=N bonds catalyzed by over 100 ruthenium hydride complexes in organic and aqueous media can be classified into two main classes: the hydride transfer step is inner sphere (I) or outer sphere (O). Important subclasses of these mechanisms are cases where an ancillary ligand may assist in the hydride transfer step (IL or OL, respectively). The types of hydride complexes and their reactivity toward C=O (ketones, aldehydes, CO2) and C=N (imines) bonds is examined. Features of the different types of catalytic cycles are described. It is clear that the ligand assisted cases lead to very efficient catalysts for the selective hydrogenation of these polar bonds (e.g. Noyori’s metal-ligand bifunctional catalysis).

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Chiral Catalysts,
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The design of second generation MOP-phosphonites: Efficient chiral hydrosilylation of functionalised styrenes

A series of enantiopure MOP-phosphonite ligands, with tailored steric profiles, have been synthesised and are proven to be very successful in high-yielding, regio- and enantioselective catalytic hydrosilylation reactions of substituted styrenes, affording important chiral secondary alcohols.

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Chiral Catalysts,
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Self-Assembly of a Highly Emissive Pure Organic Imine-Based Stack for Electroluminescence and Cell Imaging

We demonstrated that a purely organic stack, namely, TPE-3-stack, can be assembled in high yield by using dynamic imine chemistry. TPE-3-stack emits strong fluorescence not only in the solid state (I?PL = 83%) but also in dilute solutions (e.g., I?PL = 82% in DMSO), which is significantly distinct from the case of the aggregation-caused quenching (ACQ) and aggregation-induced emission (AIE) chromophores. In addition, it shows high spectral, thermal, and chemical stabilities as well as excellent solubility in common solvents. Therefore, this stack is feasible for fabricating a solution-processed electroluminescent device, which displays brightness over 1000 cd m-2 and a current efficiency up to 2.3 cd A-1. TPE-3-stack is also demonstrated as a promising fluorescent visualizer for lysosome imaging. Such characteristics of the stack compound were attributed to the efficient suppression of intramolecular rotation and vibration by locking its structure into the rigid framework by means of a self-assembly strategy.

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Chiral Catalysts,
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A bifunctional PdVMgO solid catalyst for the one-pot selective N-monoalkylation of amines with alcohols

It has been found that a bifunctional metal Pd/base (MgO) catalyst performs the selective monoalkylation of amines with alcohols. The reaction goes through a series of consecutive steps in a cascade mode that involves: 1) the abstraction of hydrogen from the alcohol that produces the metal hydride and the carbonyl compound; 2) condensation of the carbonyl with the amine to give an imine, and 3) hydrogenation of the imine with the surface hydrogen atoms from the metal hydride. Based on isotopic and spectroscopic studies and on the rate of each elementary step, a global reaction mechanism has been proposed. The controlling step of the process is the hydride transfer from the metal to the imine. By changing the crystallite size of the Pd, it is demonstrated that this is a structure-sensitive reaction, whereas the competing processes that lead to subproducts are not. On these bases, a highly selective catalyst has been obtained with Pd crystallite size below 2.5 nm in diameter. The high efficiency of the catalytic system has allowed us to extend the process to the one-pot synthesis of piperazines.

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Chiral Catalysts,
Chiral catalysts – SlideShare

 

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Carbon dioxide as a carbonylating agent in the synthesis of 2-oxazolidinones, 2-oxazinones, and cyclic ureas: Scope and limitations

Carbon dioxide can be used as a convenient carbonylating agent in the synthesis of 2-oxazolidinones, 2-oxazinones, and cyclic ureas. The transient carbamate anion generated by treating a primary or secondary amine group in basic media can be activated with phosphorylating agents such as Diphenylphosphoryl azide (DPPA) and Diphenyl chlorophosphate (DPPCl) but also with other types of electrophiles such as SOCl2, TsCl, or AcCl. The intramolecular trapping of the activated carbamate by a hydroxyl group leads to the formation of 2-oxazolidinones or 2-oxazinones in good to excellent yields. This methodology was successfully applied to the synthesis of cyclic ureas up to 7-membered rings from the corresponding diamines.

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Chiral Catalysts,
Chiral catalysts – SlideShare