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A new optically active diphosphine ligand, [(5,6),(5?,6?)-bis(ethylenedioxy)biphenyl.2,2?-diyl]bis (diphenylphosphine) (SYNPHOS) has been synthesized. Laboratory-scale synthesis and scale-up development of this ligand are described herein. This new atropisomeric diphosphine was also used in ruthenium-catalyzed asymmetric hydrogenation.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Alcohols, in particular polyols, are well-known for the synthesis of metal nanoparticles, often acting as reducing agents, solvents, and stabilizers. Given not only their structural flexibility depending on the number of OH functions and their inherent H bonding interactions, but also the wide range of polyol molecular weights readily available, different physicochemical properties (boiling point, polarity, viscosity) could be exploited toward the synthesis of well-defined nanomaterials. In particular, the relevance of the supramolecular structure of polyols has a fundamental impact on the formation of metal nanoparticles, thereby favoring the dispersion of the nanoclusters. In the field of the metal-based nanocatalysis, palladium occupies a privileged position mainly due to its remarkable versatility in terms of reactivity representing a foremost tool in synthesis. In this review, we describe the controlled synthesis of Pd-based nanoparticles in polyol medium, focusing on the progress in terms of tailoring size, morphology, structure, and surface state. Moreover, we discuss the use of palladium nanoparticles, in a polyol solvent, applied in two of the most relevant Pd-catalyzed processes, i.e., couplings and hydrogenation reactions, including multistep processes.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The enantioface-differentianing hydrogenation of 4-hydroxy-2-butanone (I) to 1,3-butanediol (II) was conduced with asymmetrically modified metal catalysts.Among the modified catalysts examined, Raney nickel modified with a solution containing tartaric acid and NaBr (TA-NaBr-MRNi) gave the best results with respect to the optical and chemical yields. (R)-II, an optical purity of 69 percent was obtained in a quantitative chemical yeld by the use of (R,R)-TA-NaBr-MRNi. (S)-II was also obtained by the use of (S,S)-TA-NaBr-MRNi.A simple method for the preparation of optically pure (S)- and (R)-II from the hydrogenation product was also developed.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Stereoselective synthesis of diplodialides-B and C and the formal synthesis of diplodialide-A are reported. A combination of Jacobsen’s hydrolytic kinetic resolution and Sharpless epoxidation is used for the creation of two stereogenic centers, while a ring-closing metathesis strategy was used for the construction of the lactone ring.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Mesomorphic, sorption, and selective properties of a three-component sorbent based on a mixture of nematic (N) liquid crystals of 4-methoxy-4?-ethoxyazoxybenzene (MEAB) and 4,4?-diethoxyazoxybenzene (azoxyphenetol, AOP) of an eutectic composition and heptakis-(2,3,6-tri-O-benzoyl)-beta-cyclodextrin (Bz-beta-CD) are studied. For 30 organic compounds of different classes with linear and cyclic molecular structures, including optical isomers of limonene, pinene, camphene, and butanediol-2,3, thermodynamic functions are determined for their gas-phase sorption using a three-component MEAB-AOP-Bz-beta- CD sorbent (62: 28: 10 wt %). It is found that the investigated sorbent possesses high structural selectivity (alphap/m = 1.128-1.059, 100-130C, N) and moderate enantioselectivity (1.07-1.02) within a broad temperature range (95-170C) including both mesomorphic and isotropic phases of the sorbent. It is shown that the enantioselectivity of the sorbent is apparent under conditions of both increasing retention when a chiral Bz-beta-CD additive is introduced into the MEAB-AOP system (limonenes, pinenes, camphenes) and decreasing retention (butanediols-2,3).

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The Arbuzov reaction of (2S,4S)-methyl-2-phenyl-1,3,2-dioxaphosphorinane with various alkyl halides gave the diastereomerically pure phosphinates with regioselective cleavage of the primary carbon-oxygen bond.These phosphinates reacted with Grignard reagents to give optically active phosphine oxides in high optical yields.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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There and back again: Hydrogenation of esters and the reverse reaction of dehydrogenative coupling of alcohols are efficiently catalyzed by dimeric complexes of Ru and Os under neutral conditions. The Os dimer (see picture) is an outstanding catalyst for the hydrogenation of alkenoates and triglycerides, and allows production of fatty alcohols from olive oil. This complex converts ethanol into ethyl acetate and hydrogen under reflux. Copyright

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Provided herein are myeloid cell leukemia 1 protein (Mcl-1) inhibitors, methods of their preparation, related pharmaceutical compositions, and methods of using the same. For example, provided herein are compounds of Formula I, (I) and pharmaceutically acceptable salts thereof and pharmaceutical compositions containing the compounds. The compounds and compositions provided herein may be used, for example, in the treatment of diseases or conditions, such as cancer.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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In the presence of BF3*Et2O, organocopper and cuprate reagents promote the substitution of one alkoxy group of an acetal.Under the same conditions, alkoxy tetrahydropyrans react selectively, by ring cleavage.Chiral cyclic acetals, having a C2 axis of symmetry are diastereoselectively cleaved.The method serves to synthesize chiral secondary alcohols, after the removal of the chiral auxiliary.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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By means of 17O NMR spectroscopy a large series of mono- and polycyclic aromatic ketones was studied in DMSO medium.A linear correlation between chemical shifts of the carbonyl group in 13C and 17O NMR spectra was found.We have established that the 17O chemical shift in ketones in their ordinary state reflects a tendency for reduction in basicity with decrease of the electronic density at the oxygen atom.It is shown that the basicity of aromatic ketones is affected by the degree of delocalization of ?-electron density both in the neutral and in the protonated form, and also by steric effects.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate