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C2-symmetric bis(sulfonamide) ligands derived from chiral trans-(1R,2R)-cyclohexane-1,2-diamine were immobilized on silica gel and on polystyrene resin, and complexed to RhIIICp*. The resulting complexes were used as catalysts in the asymmetric transfer hydrogenation (ATH) of acetophenone. The chiral secondary alcohol was obtained in high yields (>99%) and enantioselectivities (92%) with aqueous sodium formate as the hydride source. The immobilized catalysts were recycled with no loss in activity.

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

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 20439-47-8, molcular formula is C6H14N2, introducing its new discovery. category: catalyst-ligand

A series of platinum(II) complexes of formulae cis-[Pt(Am) 2X2] (where Am represents an inert amine and X a labile (carboxylato) ligand) have been prepared and characterized by elemental analysis, ESI-MS, IR and 1H NMR spectroscopy. The single-crystal molecular structures were determined for cis-[Pt(opea)(cbdca-2H)], cis-[Pt(hmpy)(cbdca-2H)], cis-[Pt(NH3)2(bzmal-2H)] and cis-[Pt(hmpy)(mu-dcch-2H)2] (where opea is picolylamine, hmpy represents 4-hydroxymethylpyridine, cbdca-2H, is 1,1-cyclobutanedicarboxylate anion, bzmal-2H stands for benzylmalonate anion and dcch-2H is trans-1,2-cyclohexanedicarboxylate anion). The interaction of all compounds with DNA was investigated with different techniques: viscosity measurements and emission fluorescence spectroscopy were used to investigate the changes induced by the binding of the platinum compounds to calf-thymus DNA, while atomic force microscopy and electrophoretic mobility allowed evaluating the potential alterations of pBR322 plasmid DNA. The cytotoxic behavior of the platinum compounds on human leukemia HL-60 tumor cell lines was also examined.

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

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Mannich-type reactions of a chiral bicyclic imine and various nucleophiles yield the corresponding adducts with good to high diastereoselectivity. The influence of the reaction conditions on the yield and stereochemical outcome is investigated. The configuration of the products is established by 1H NMR spectroscopy, and the major isomers of two adducts are characterized by X-ray crystallography.

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

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The chiral SalenCo(III)OAc-catalyzed hydrolytic kinetic resolution (HKR) of racemic terminal epoxides to afford both enantioenriched epoxides and diols presents one of the most important achievements in asymmetric synthesis chemistry. Previous studies mainly focused on the development of highly efficient catalysts, while rare reports concerned the mechanistic understanding of metal valence change, associated with the formation of inactive Co(II)-Salen complex. Herein, we report the mechanistic aspects of catalyst deactivation regarding the transformation of Co(III) to Co(II) derivative in the HKR of racemic epoxides catalyzed by SalenCo(III)OAc complexes with an appended 1,5,7-triazabicyclo[4.4.0]dec-5-ene on the ligand framework by means of electrospray ionization mass spectrometry (ESI-MS). Continuous determination of transient cationic species in ESI-MS positive mode in conjunction with UV-vis spectroscopic studies at various time points provides evidence that a certain amount of SalenCo(III)OAc molecules were reduced to the corresponding Co(II) derivatives in the HKR of racemic propylene oxide or styrene oxide. To be accompanied by the reduction of Co(III) to Co(II), the resultant diols were oxidized to alpha-hydroxy ketones. These analyses along with some control experiments gave a mechanistic understanding of catalyst deactivation of SalenCo(III)OAc-catalyzed HKR of racemic epoxides regarding an unveiled redox reaction between Co(III)-Salen and diol, the hydrolyzed product.

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

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A new chiral bis-thiourea-type organocatalyst 2 developed for the Baylis-Hillman reaction provided a drastic rate enhancement. Allylic alcohols were obtained with up to 90% ee in the case of cyclohexanecarboxaldehyde (4i).

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

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The two enantiomers of trans-1,2-diaminocylohexane form well-defined supramolecular structures with appropriately paired C2 symmetrical 1,2-diols that are assembled by H-bonding. Depending on the structure and chirality of the diol, it is possible to form left- or right-handed trihelicate structures consisting of polar cores and hydrophobic outer residues. These structures can be sublimed without change, and they slowly adsorb carbon dioxide to eventually give polymeric amorphous fibers. Heating these materials regenerates the original 1:1 adducts as supramolecular entities. The parent diamines can be converted into crystalline carbamate salts which exist as layered trihelicate structures. Other charged supramolecular structures are formed from the (R,R)-diamine and the enantiomeric tartaric acids. The diamine molecule appears to be a superb assembler of neutral and charged supramolecular structures by accommodating preferred diol and acid partners in its crystal lattice. Molecular recognition and self-assembly are based on non-amidic H-bonding between amine and alcohol functions in the neutral molecules, leading to supramolecular structures whose helicity mode depends on the sense of chirality of the diamine used. All the reported structures were characterized by single-crystal X-ray analysis.

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

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A clean and efficient reductive intramolecular coupling of diimines prepared from (1R,2R)-cyclohexanediamine gave chiral 2,3-diarylpiperazines.

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

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Flexible redox properties of a metal complex are important for redox catalysis. The present study shows that the reaction of a manganese(III) salen complex, which is a well-known oxidation catalyst, with hydroxide ion gives a transient manganese(III) species with drastically lowered redox potential, where the redox difference is -1.21 V. The reaction with cyanide ion gives a stable manganese(III) species with almost the same spectroscopic and redox properties, which was characterized as an anionic [MnIII(salen)(CN)2]- of low-spin S = 1 state, in contrast to the starting MnIII(salen)(OTf) having usual high-spin S = 2 manganese(III). The present study has thus clarified that the drastic redox shift comes from an anionic six-coordinate [MnIII(salen)(X)2]- species where X is either OH- or CN-. Resonance Raman measurements show that the stretching band of the imino group shifts from 1620 to 1597 cm-1 upon conversion from MnIII(salen)(OTf) to [MnIII(salen)(CN)2]-, indicative of lowered C=N double bond character for [MnIII(salen)(CN)2]-. The observed deformation of a salen ligand is a clear indication of an increased electron population on the imino pi?-orbital upon formation of low-spin manganese(III). It was proposed that the electronic structure of [MnIII(salen)(CN)2]- may contain only limited contribution from valence tautomeric [MnIV(salen-Ȣ)(CN)2]-, in which the imino group of a salen ligand is reduced by one-electron via intramolecular electron transfer from low-spin manganese(III). The present study has clarified an unexpected new finding that a salen ligand works as a reservoir for negative charge to stabilize low-spin manganese(III).

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

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The efficient synthesis of large-ring pseudopeptidic macrocycles through a multicomponent [2 + 2] reductive amination reaction is described. The reaction was entirely governed by the structural information contained in the corresponding open-chain pseudopeptidic bis(amidoamine) precursors, which have a rigid (R,R)-cyclohexane-1,2-diamine moiety. A remarkable match/mismatch relationship between the configurations of the chiral centers of the cyclic diamine and those of the peptidic frame was observed. The macrocyclic tetraimine intermediates have been studied in detail by NMR spectroscopy, circular dichroism (CD), and molecular modeling, and the results support the appropriate preorganization induced by the match combination of the chiral centers. We have also synthesized the corresponding open-chain bis(imine) model compounds. The structural studies (NMR spectroscopy, CD, modeling) of these systems showed an intrinsically lower reactivity of the mismatch combination, even when the product of the reaction was acyclic. In addition, a synergistic effect between the two chiral substructures for the correct folding of the molecules was observed. Finally, X-ray analysis of the HCl salt of one of the macrocycles showed an interesting pattern; the macrocyclic rings stack in columnar aggregates leaving large interstitial channels filled with water-solvated chloride anions.

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

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Rhombimines, chiral macrocyclic tetraimines, are preferentially formed because of the structural bias in the reaction of aromatic ether-linked dialdehydes with enantiomerically pure trans-1,2-diaminocyclohexane.

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