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Chiral macrocyclic CrIII salen complexes have been synthesized, characterized, and used as catalysts in the asymmetric aminolysis of aromatic ester epoxides with various anilines to prepare the beta-amino-alpha-hydroxyl esters in very good yield (up to 95 %) along with high diastereo- and enantioselectivity (dr>99/1, ee up to 96 %) under the optimized condition particularly with CrIII complex 4, which was effectively recycled four times.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Amino-functionalized sulfonimidamides have been prepared by aziridinium ring-opening reactions and nucleophilic substitutions of sulfonimidoyl chlorides. Whereas the former reactions afford separable diastereomeric products, the latter provide single stereoisomers. Application of the resulting stereochemically homogeneous sulfonimidamides as ligands in asymmetric copper-catalyzed Henry reactions of aromatic aldehydes with nitromethane led to products with enantioselectivities up to 95% ee in good yields.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The synthesis of series of D2h and C2v symmetric oxygenated aromatic dicarboxaldehydes, using dilithiation methodology, is described along with their reactivity in the [3 + 3] cyclocondensation reaction with (1R,2R)-diaminocyclohexane to give oxygenated trianglimine macrocycles. Macrocycles derived from C2v symmetric dialdehydes give macrocycles with a stereogenic aromatic plane with complete diastereocontrol, as a mixture of retainers.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A series of novel C-5 arylated calixsalens synthesized via [3+3] cyclocondensation of trans-(R,R)-1,2-diaminocyclohexane with 2-hydroxyisophthalaldehyde derivatives are presented. The nonsymmetrical aryl substituents of the 1-naphthyl type may act as switches opening (ON conformation) or closing (OFF conformation) the macrocycle cavity. This group of macrocycles, depending on the kind of aryl substituent, is characterized by a large variety of supramolecular architectures. Whereas the substitution of the calixsalen skeleton by 2,5-dimethoxybenzene groups promotes the formation of head-to-head capsules, the presence of a 3,5-dimethylbenzene group favors the tail-to-tail dimers. Introduction of 2-naphthyl substituents, in turn, results in the formation of a supramolecule consisting of four monomers that exists only in the solid state. Such arrangements of macrocycles generate a truncated tetrahedron shaped cavity never previously observed for this type of macrocyclic compounds.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chiral ligands 8-11, 22 and 23 were synthesized from different chiral diamines as a new class of ligands for the Pd(II)-catalyzed 1,4-diacetoxylation of 1,3-dienes. The synthesis from the diamines and protected benzoic acids was performed in a few simple steps and gave the ligands in high overall yields. The hydroquinone groups present in the ligands are in situ oxidized to benzoquinone to give the active ligands. Application of these ligands in the 1,4-diacetoxylation reaction afforded the oxidation product with high regio- and diastereoselectivity and an enantiomeric excess up to 42% was obtained. Possible coordination modes of the metal to the ligand are discussed, and experiments were made to investigate the coordination by varying the reaction conditions or making changes to the ligands.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Salen’ along: The iridium(III)-salen complex 1 efficiently catalyzes the title reaction of 2-ethylbenzenesulfonyl azides to give five-membered sultams with high enantioselectivity. Other 2-alkyl-substitued substrates lead to five- and six-membered sultams with high enantioselectivity; the regioselectivity depends upon the substrate and the catalyst used. EDG=electron-donating group. Copyright

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Characterisation of the products of reactions of the Co(III) complex of a quadridentate amine incorporating an azetidine ring by structural crystallography has shown the bound heterocyclic ring to be stable under quite forcing conditions. With bidentate co-ligands, the tetramine appears to prefer one form of “cis-beta” coordination to Co(III). On Cu(II), the tetramine is readily and stereoselectively converted to a macrocycle which may be a useful precursor to pendent-arm derivatives.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A palladium-catalyzed intramolecular alpha-arylation and defluorinative aromatization strategy for the synthesis of polysubstituted 2-naphthols is reported. With ortho-bromobenzyl-substituted alpha-fluoroketones as the substrates and palladium acetate/triphenylphosphine as the catalyst, this method features good functional group tolerance, readily available catalyst and starting materials, and high yields. The applications of the strategy are demonstrated by the synthesis of useful building blocks, such as naphtha[2,3-b]furan, naphthol AS-D, and ligands/catalysts. (Figure presented.).

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The diastereospecific formation of dihydropyrimidines (DHPMs) has been achieved in moderate to high yields with up to 99% ee by a Biginelli reaction. The reaction was performed by using a combined catalyst consisting of a chiral bifunctional primary amine-thiourea 9f and a Bronsted acid with tert-butylammonium trifluoroacetate (t-BuNH2·TFA) as additive in dichloromethane at room temperature. The possible mechanism for the reaction has been proposed to explain the origin of the activation and the asymmetric induction.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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In this work, the new polysaccharide-platinum conjugates of 5-aminosalicylic acid modified lycium barbarum polysaccharide linking platinum compounds were designed in order to construct an anticancer metal drug delivery system. The multiple analysis methods were used to describe the chemical structure and physical properties of the polysaccharide-metal conjugates. The results showed that 5-aminosalicylic acid successfully acted as linker which was covalently bound between polysaccharide and platinum compound. The morphology and rheological properties of polysaccharide have been changed by the formation of conjugates, which exhibited certain inhibition specificity to A549 (human lung cancer cell line). The agarose gel electrophoresis and fluorescence microscopy results demonstrated that such conjugates promoted the unwinding of DNA and could significantly damage the nucleus of A549 cells. Cell cycle analyzing the Pt complex of conjugates could cause intracellular DNA damage and induced G2 phase arrest. So, polysaccharide-platinum conjugates might find a range of applications, for example in metal anticancer drug delivery.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI