Discovery of (1R,2R)-Cyclohexane-1,2-diamine

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Bpytrisalen/Bpytrisaloph: A Triangular Platform That Spatially Arranges Different Multiple Labile Coordination Sites

Complexes that possess multiple metals in their proximity exert useful functions such as multivalent capture and catalytic activities. However, it is often challenging to arrange multiple metals with regular distances and to maintain the reactive coordination sites. We have now designed and synthesized organic macrocyclic ligands, bpytrisalen and bpytrisaloph, as platforms to spatially arrange different kinds of metals and their coordination sites. Metals coordinating to the bpy N2 units of the triangular ligands are assembled in the cavity with their labile coordination sites directed inward. Meanwhile, the metals at the salen/saloph N2O2 units have axial coordination sites that are vertically pointing out of the triangle. As a result, planar homo- and heterohexanuclear complexes with different kinds of coordination sites are obtained. Furthermore, a double-decker structure was selectively constructed upon coordinating a ditopic linker ligand to the axial coordination sites of the salen units, which shows the orthogonality of the coordination sites at the bpy and salen units. The consistency in the array of metal centers and their coordination sites irrespective of the elements is a desirable feature in the pursuit of applications for the multinuclear complexes.

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

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Highly Enantioselective Iron-Catalyzed cis-Dihydroxylation of Alkenes with Hydrogen Peroxide Oxidant via an FeIII-OOH Reactive Intermediate

The development of environmentally benign catalysts for highly enantioselective asymmetric cis-dihydroxylation (AD) of alkenes with broad substrate scope remains a challenge. By employing [FeII(L)(OTf)2] (L=N,N?-dimethyl-N,N?-bis(2-methyl-8-quinolyl)-cyclohexane-1,2-diamine) as a catalyst, cis-diols in up to 99.8 % ee with 85 % isolated yield have been achieved in AD of alkenes with H2O2as an oxidant and alkenes in a limiting amount. This ?[FeII(L)(OTf)2]+H2O2? method is applicable to both (E)-alkenes and terminal alkenes (24 examples >80 % ee, up to 1 g scale). Mechanistic studies, including18O-labeling, UV/Vis, EPR, ESI-MS analyses, and DFT calculations lend evidence for the involvement of chiral FeIII-OOH active species in enantioselective formation of the two C?O bonds.

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

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Asymmetric Henry reaction catalyzed by chiral secondary diamine-copper(II) complexes

The enantioselective Henry reaction was efficiently carried out under mild reaction conditions in 96% ethanol. The chiral C2-symmetric, secondary bisamines based on the 1,2-diaminocyclohexane framework and copper(II) acetate were found to promote the asymmetric nitroaldol reaction. Aromatic and aliphatic aldehydes were reacted with nitromethane to provide the corresponding beta-nitroalcohols in very good yields and enantioselectivities up to 94%.

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

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Multifunctional Tubular Organic Cage-Supported Ultrafine Palladium Nanoparticles for Sequential Catalysis

The imine condensation reaction of 5,5?-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diisophthalaldehyde with cyclohexanediamine resulted in a shape-persistent multifunctional tubular organic cage (MTC1). It exhibits selective fluorescence sensing towards divalent Pd ions with a very low detection limit (38 ppb), suggesting effective complexation between these two species. Subsequent reduction of MTC1 and Pd(OAc)2 with NaBH4 afforded a cage-supported catalyst with well-dispersed ultrafine Pd nanoparticles (NPs) in a narrow size distribution (1.9¡À0.4 nm), denoted as PdaMTC1-1/5. Such ultrafine Pd NPs in PdaMTC1-1/5, in cooperation with photocatalytically active MTC1, enable efficient sequential reactions involving visible light-induced aerobic hydroxylation of 4-nitrophenylboronic acid to 4-nitrophenol and the following hydride reduction with NaBH4. This is the first example of a multifunctional organic cage capable of sensing, directing nanoparticle growth, and catalyzing sequential reactions.

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

Extracurricular laboratory:new discovery of (1R,2R)-Cyclohexane-1,2-diamine

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CONTROLLED RELEASE OF ACTIVE ALDEHYDES AND KETONES FROM EQUILIBRATED DYNAMIC MIXTURES

The present invention concerns a dynamic mixture obtained by combining, in the presence of water, at least one diamine derivative, comprising at least one benzylamine moiety, with at least one active aldehyde or ketone. The invention’s mixture is capable of releasing in a controlled and prolonged manner said active compound, in particular perfuming ingredients, in the surrounding environment.

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

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Enantioselective [2,3]-wittig rearrangement via a chiral boron ester enolate

The first enantioselective [2,3]-Wittig rearrangement of alpha-(allyloxy)- acetates is described which involves a chiral boron enolate with a chiral bis-suifonamide ligand to afford the alpha-hydroxy-beta-alkyl-gamma,delta-unsaturated esters in a high enantioselectivity (>95%ee), along with a high threo diastereoselectivity.

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

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BISPHOSPHONATE COMPLEXES

Bisphosphonate compounds are disclosed, particularly bisphosonate conjugates useful in the treatment of soft tissues surrounding bone and bone-related diseases, such as bone cancer and osteoporosis.

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

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Accurate chiral pattern recognition for amines from just a single chemosensor

The current work proposes a novel determination method for enantiomeric excess (ee) in (mono- and di-) amines using molecular self-assembly. A pyridine-attached binaphthyl derivative ((R)-1) exhibits fluorescence responses based on imine formation between the aldehyde group of (R)-1 and target chiral amines (i.e. cyclohexane diamine (CHDA), 2-amino-1,2-diphenylethanol (ADPE), 1,2-diphenylethylenediamine (DPDA), 1-amino-2-indanol (AID), and leucinol) in the presence of zinc(ii) ions (Zn2+). Because of the multi-optical responses which are derived from the variation of chiral complexes, pattern recognition-based discrimination (i.e. linear discriminant analysis (LDA)) has been achieved for five types of enantiomeric pairs of amines. Possessing such a discrimination capability in combination with data processing (LDA and an artificial neural network) allows accurate determination (prediction error < 1.8%) of the % ee of individual targets such as CHDA which is one of the main components of pharmaceutical drugs. The simple molecular self-assembled system enabled simultaneous multi-chiral discrimination and % ee determination of unknown samples. Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions.Recommanded Product: 20439-47-8, you can also check out more blogs about20439-47-8

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

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Mechanism and scope of salen bifunctional catalysts in asymmetric aldehyde and alpha-ketoester alkylation

Metal complexes of C2-symmetric Lewis acid/Lewis base salen ligands provide bifunctional activation resulting in rapid rates in the enantioselective addition of diethylzinc to aldehydes (up to 92% ee). Further experiments probed the reactivity of the individual Lewis acid and Lewis base components of the catalyst and established that both moieties are essential for asymmetric catalysis. These catalysts are also effective in the asymmetric addition of diethylzinc to alpha-ketoesters. This finding is significant because alpha-ketoesters alone serve as their own ligands to accelerate racemic 1,2-carbonyl addition of Et2Zn and racemic carbonyl reduction. The latter proceeds via a metalloene pathway, and often accounts for the predominant product. Singular Lewis acid catalysts do not accelerate enantioselective 1,2-addition over these two competing paths. The bifunctional amino salen catalysts, however, rapidly provide enantioenriched 1,2-addition products in excellent yield, complete chemoselectivity, and good enantioselectivity (up to 88% ee). A library of the bifunctional amino salens was synthesized and evaluated in this reaction. The utility of the alpha-ketoester method has been demonstrated in the synthesis of an opiate antagonist.

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

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Highly Acidic Conjugate-Base-Stabilized Carboxylic Acids Catalyze Enantioselective oxa-Pictet?Spengler Reactions with Ketals

Acyclic ketone-derived oxocarbenium ions are involved as intermediates in numerous reactions that provide valuable products, however, they have thus far eluded efforts aimed at asymmetric catalysis. We report that a readily accessible chiral carboxylic acid catalyst exerts control over asymmetric cyclizations of acyclic ketone-derived trisubstituted oxocarbenium ions, thereby providing access to highly enantioenriched dihydropyran products containing a tetrasubstituted stereogenic center. The high acidity of the carboxylic acid catalyst, which exceeds that of the well-known chiral phosphoric acid catalyst TRIP, is largely derived from stabilization of the carboxylate conjugate base through intramolecular anion-binding to a thiourea site.

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