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IRON CATALYSTS WITH UNSYMMETRICAL PNN’P LIGANDS

The present invention relates to catalytic materials for hydrogenation or asymmetric hydrogenation. In particular, the invention relates to iron (II) complexes containing unsymmetrical tetradentate diphosphine (PNN’P) ligands with two different nitrogen donor groups useful for catalytic transfer hydrogenation or asymmetric transfer hydrogenation of ketones, aldehydes and imines.

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

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Matching the chirality of monodentate N-heterocyclic carbene ligands: A case study on well-defined palladium complexes for the asymmetric alpha-arylation of amides

(Chemical Equation Presented) N-Heterocyclic carbene ligands derived from C2-symmetric diamines with naphthyl side chains are introduced as chiral monodentate ligands, and their palladium complexes (NHC)Pd(cin)C) are prepared. These compounds exist as a mixture of diastereomers, and the palladium complexes can be successfully separated and their absolute stereochemistry assigned. When used in the asymmetric intramolecular alpha-arylation of amides, oxindoles with quaternary carbon centers can be obtained in high yield and selectivity when correctly matching the chirality of the NHC complexes.

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

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Rhodium(I) bisaldimine complexes in transfer hydrogenation

The reactions of hydrogen transfer from 2-propanol on acetophenone in the presence of the system [Rh(cod)Cl]2?L] (L is bisaldimine ligands based on (R,R)-1,2-cyclohexanediimine and pyridine-, quinoline-, and thiophenecarboxaldehyde) were studied. Rhodium(I) complexes with optically active ligand showed a high catalytic activity (up to 345 h?1) and moderate enantioselectivity [up to 55% ee of (R)-1-phenyethanol]. The structure of rhodium complex with N,N’-(1R,2R)-cyclohexane-1,2-diyl-bis[1-(pyridine-2-yl)methanimine] was determined on the basis of the data of 1H and 13C NMR spectroscopy and quantum chemical calculations.

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

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Simultaneous determination of both the enantiomeric composition and concentration of a chiral substrate with one fluorescent sensor

A fluorescent sensor is discovered to exhibit high sensitivity at one emission wavelength and high enantioselectivity at another when treated with a chiral diamine. By using this fluorescent sensor, it is demonstrated for the first time that both the concentration and enantiomeric composition of a chiral substrate can be determined simultaneously with one fluorescence measurement.

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Metal catalyst and ligand design,
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Monoimine derived from trans-1,2-diaminocyclohexane and ethyl glyoxylate: An intermediate in aza-Diels-Alder and Mannich reactions

Novel enantiopure policyclic nitrogen heterocycles have been obtained in the diastereoselective aza-Diels-Alder or Mannich reaction of dienes with imine formed in situ from ethyl glyoxylate and (1R,2R)-diaminocyclohexane.

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

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Synthesis and in vitro antiplasmodial activity of ferrocenyl aminoquinoline derivatives

The aim of this study was to synthesize a series of ferrocenyl 4-aminoquinolines and to evaluate their activities against Plasmodium falciparum F32 (chloroquine-sensitive) and FCB1 and K1 (chloroquino-resistant). Some of the ferrocenyl compounds exhibited in vitro antiplasmodial activity in the nM range. In particular, (1R,4R)-N1-(7-chloroquinolin-4-yl)-N4-(ferrocenylmethyl)-N4-methylcyclohexane-1,4-diamine 17 presented the lowest IC50 value (26 nM) against CQ-resistant strains.

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Metal catalyst and ligand design,
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A “chirality driven self-sorting” strategy is introduced for the controlled supramolecular organization of donor (D) and acceptor (A) molecules in multicomponent assemblies. The trans-1,2-bis(amido)cyclohexane (trans-BAC) has been identified as a supramolecular motif with strong homochiral recognition to direct this chirality controlled assembly process of enantiomers in solution. Stereoselective supramolecular polymerization of trans-BAC appended naphthalene diimide monomers (NDIs) has been probed in detail by spectroscopic and mechanistic investigations. This chirality-driven self-sorting design of enantiomeric components also offers to realize mixed and segregated D-A stacks by supramolecular co-assembly of the NDI acceptors with trans-BAC appended dialkoxynaphthalene (DAN) donor monomers. Such an unprecedented chirality control on D-A organization paves the way for the creation of supramolecular p-n nanostructures with controlled molecular-level organization. Chiral stacking: A chirality-driven self-sorting strategy has been introduced for the construction of mixed and segregated donor-acceptor supramolecular arrays in solution.

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A modular approach was developed for the preparation of chiral, enantiopure sulfonamide ligands with C1, C2, and C3 symmetry by ring opening of chiral N-sulfonylaziridines with ammonia, primary amines, and diamines. The new ligands were assessed in the titanium-mediated addition of diethylzinc to benzaldehyde, giving the product with selectivities up to 76% ee. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

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

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Direct Formation of Oxocarbenium Ions under Weakly Acidic Conditions: Catalytic Enantioselective Oxa-Pictet-Spengler Reactions

Two catalysts, an amine HCl salt and a bisthiourea, work in concert to enable the generation of oxocarbenium ions under mild conditions. The amine catalyst generates an iminium ion of sufficient electrophilicity to enable 1,2-attack by an alcohol. Catalyst turnover is achieved by amine elimination with concomitant formation of an oxocarbenium intermediate. The bisthiourea catalyst accelerates all of the steps of the reaction and controls the stereoselectivity via anion binding/ion pair formation. This new concept was applied to direct catalytic enantioselective oxa-Pictet-Spengler reactions of tryptophol with aldehydes.

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

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Synthesis and characterization of chiral nitrobenzaldehyde – Schiff base ligands

Three chiral nitrobenzaldehyde/Schiff base ligands (2a-c) were prepared by the reaction of ortho, meta, and para-NO2 substituted benzaldehydes (1a-c) with (1R,2R)-(-)-1,2-diaminocyclohexane. The structures of ligands 2a-c were characterized by IR, 1H-NMR, 13C-NMR and elemental analysis.

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