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Novel chiral C2-symmetric bisimidazole-N-oxides as promising organocatalysts for enantioselective allylation of aromatic aldehydes

A series of new, chiral Lewis bases containing imidazole-N-oxide moiety were tested for purposes of asymmetric catalysis. Bisimidazole-N-oxides derived from (1R,2R)- and (1S,2S)-trans-1,2-diaminocyclohexane were used as catalysts in the allylation reaction of aromatic aldehydes with allyltrichlorosilane, which yielded homoallyl alcohols in good yields and with enantioselectivity up to 80% ee. Screening of catalysts revealed that the type of substituents and their location in imidazole ring has a crucial influence on enantioselectivity of the addition process. Georg Thieme Verlag Stuttgart.

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Compounds formed by Mannich reaction of a coordinated amine with an alpha-methylene nitro compound and formaldehyde ? Syntheses and structures

This review covers compounds formed by Mannich-like reactions of coordinated amine-compounds with an alpha-methylene nitro-compound (usually nitroethane) and an aldehyde (predominantly formaldehyde) to form a compound with two primary amine functions joined by a ?NH?(CH2)?C(NO2)(CH3)?(CH2)?NH? link, forming a new chelate ring. Most reported compounds have tetraaza-macrocyclic ligands. Copper(II) is the usual ?templating? metal ion, with compounds of nickel(II), palladium(II), platinum(II) and gold(III) also reported. The refcodes of compound with structures in the Cambridge Crystallographic Data Centre files are listed and structural figures of representative examples shown.[Figure presented]

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Chiroptical Asymmetric Reaction Screening via Multicomponent Self-Assembly

Self-assembly of a stereodynamic phosphine ligand, Pd(II), and a chiral amine, amino alcohol, or amino acid generates characteristic UV and CD signals that can be used for quantitative stereochemical analysis of the bound substrate. A robust mix-and-measure chiroptical sensing protocol has been developed and used to determine the absolute configuration, ee, and yield of an amine produced by Ir-catalyzed asymmetric hydrogenation of an iminium salt. The analysis requires only 1 mg of the crude reaction mixture and minimizes cost, labor, time, and waste.

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Brightly Luminescent and Kinetically Inert Lanthanide Bioprobes Based on Linear and Preorganized Chelators

The synthesis, photophysical properties, and kinetic stability of a series of water-soluble, highly emissive Tb(III) and Eu(III) complexes featuring triethylenetetraamine hexaacetic acid (TTHA) and cyclohexyl triethylenetetraamine hexaacetic acid (cyTTHA) chelator scaffolds and carbostyril sensitizers are reported. The unique and modular design of the chelators gives rise to striking quantum yields of emission in aqueous solutions (up to 54%) as well as the characteristic lanthanides’ photophysical properties (long excited-state lifetimes, large effective Stokes shifts, and narrow emission peaks). Furthermore, the preorganized chelators (L3, L4, and L6) bind metal within minutes at ambient temperature yet exhibit substantial resistance to transchelation in the presence of a challenge solution (EDTA, 1 mM). Moreover, the Eu(III) complex of L4 remains stably luminescent in HeLa cells over hours, demonstrating the suitability of these compounds for live-cell imaging applications. Representative chelators suitable for derivatization and protein bioconjugation were also prepared that were functionalized with clickable azide and alkyne moieties, biotin, and trimethoprim (TMP). With exceptional long-wavelength brightness, enhanced kinetic inertness, and an adaptable synthetic route, the reported lanthanide complexes are promising probes and labels for time-gated bioanalysis, biosensing, and optical microscopy.

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Chiral palladium(II) and platinum(II) complexes of diaminocyclohexane: X-ray structures of (1R,2R)-(-)-1,2-diaminocyclohexane dihydrochloride and its corresponding oxalato platinum(II) complex

The nucleophilic substitution reaction of the enantiomerically pure ligand, (1R,2R)-(-)-1,2-diaminocyclohexane [DACH] (1) with cis-bis(benzonitrile)palladium(II) dichloride [(PhCN)2PdCl2] leads to the formation of the complex [(DACH)PdCl2] (2) in a high yield. The reaction of the corresponding platinum(II) complex [(PhCN)2PtCl2] with DACH, under the same reaction conditions, surprisingly, took a different course, in which nucleophilic addition to the benzonitrile ligand occurred forming an enantiomerically pure amidine complex [(PhC=NH-NH(C6H10)NH2)Pt(N?CPh)Cl]Cl (3), where the nitrogen ligand form a seven-membered chelate around the central atom. The aqua and oxalato derivatives of complex 2, [(DACH)Pd(H2O)2](NO3)2 (4) and [(DACH)Pd(C2O4)] (5) have also been prepared and characterized. The platinum analogue complex to 5, [(DACH)Pt(C2O4)] (6), was prepared starting from the enantiomerically pure isomer (1) and the platinum salt K2PtX4 (X = Cl, I). According to X-ray structural analysis carried out on the complex, the product does not consist of just the desired isomer, but a mixture of both the trans-l (trans-(-)-1R,2R) and trans-d (trans-(+)-1S,2S) isomers. No retention of optical isomerism was observed. The single crystal structural analysis was also carried out on the ligand N,N?-(1R,2R)-(-)-diaminocyclohexane dihydrochloride (DACH-2HCl)] (1a). The result indicates, however, that only the R,R-isomer exists in the free ligand.

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Chiral cobalt(II)-salen-catalyzed Michael addition of amines to beta-substituted nitroalkenes

Optically active cobalt(II) salen complexes were found to be effective Lewis acid catalysts for the enantioselective Michael addition of O-alkylhydroxylamines to nitroalkenes to afford the corresponding N-alkylhydroxyl-1,2-nitroamines in high yields and with good to high enantioselectivities. This study represents the first example of a transition-metal-catalyzed asymmetric Michael addition of amines to nitroalkenes.

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Chiral macrocyclic N2P2 ligands and Iron(II): A marriage of interest

The N2P2 macrocyclic ligands (5S,8S,13E,14aS,18aS, 19E)-5,8-diphenyl-5,6,7,8,14a,15,16,17,18,18a-decahydrotribenzo[b,f,l][1,4,8,11] diazadiphosphacyclotetradecine ((1S,4S,9S,10S)-1a) and (5E,7R,8R,9E,15S,18S)-7, 8,15,18-tetraphenyl-7,8,15,16,17,18-hexahydrodibenzo[f,l][1,4,8,11] diazadiphosphacyclotetradecine ((1S,4S,9R,10R)-1b) were prepared by condensing the new, enantiomerically pure synthon 2,2?-((1S,1?S)-ethane-1,2- diylbis(phenylphosphinediyl))dibenzaldehyde ((S,S)-8), prepared in six steps from (2R,4S,5R)-3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine-2-borane (3)), with (1S,2S)-cyclohexane-1,2-diamine and (1R,2R)-1,2-diphenylethane-1,2- diamine under high-dilution conditions. The opposite enantiomers of the diamines gave oligomeric products. The stereospecificity of the macrocyclization reaction is explained by conformational analysis based on the X-ray structures of (1S,4S,9S,10S)-1a and (1S,4S,9R,10R)-1b. The corresponding diamino macrocycles (1S,4S,9S,10S)-2a and (1S,4S,9R,10R)-2b were prepared by reduction of the imine moiety of (1S,4S,9S,10S)-1a and (1S,4S,9R,10R)-1b, respectively. Macrocycles (1S,4S,9S,10S)-1a, (1S,4S,9R,10R)-1b, and (1S,4S,9S,10S)-2a react with [Fe(OH2)6](BF4)2 in acetonitrile to give the corresponding stable, diamagnetic bis(acetonitrile) complexes [Fe(MeCN)2(1)](BF4)2 (9a and 9b) and [Fe(MeCN)2(2a)](BF4)2 (10a). Complex 9a exists as a 3:1 mixture of trans and lambda-cis-beta isomers, whereas 9b and 10a adopt the lambda-cis-beta configuration exclusively. The bis(acetonitrile) complexes are versatile precursors and were used to prepare the bromocarbonyl analogues [FeBr(CO)(1)]BPh4 (11a and 11b).

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Experimental and Mechanistic Exploration of Zn-Catalyzed Sonogashira?type Cross-Coupling Reactions

One of the most straightforward methods for the synthesis of disubstituted alkynes is the transition metal catalyzed Sonogashira-type cross-coupling reactions. Herein we report a detailed study of our recent research on the first Zn-catalyzed protocol for C(sp2)?C(sp) cross-coupling reaction of aryl iodides with terminal alkynes. A wide range of functional groups were tolerated in the reaction and both functionally and structurally diverse diaryl acetylenes were prepared efficiently using this protocol. The reaction mechanism for the Zn-catalyzed Sonogashira-type coupling reaction was investigated by means of density functional theory (DFT) methods on a model system. The calculations were performed using hybrid Becke Perdew Functional (BPV86) in conjugation with LANL-2DZ basis set and found that the reaction pathway involves oxidative addition and reductive elimination mechanism.

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Enantioselective cobalt-catalyzed preparation of trifluoromethyl- substituted cyclopropanes

Easy access on water: A cobalt-catalyzed asymmetric preparation of trifluoromethylcyclopropanes has been developed that yields high enantioselectivities with a broad range of styrene substrates (see scheme). The reaction presents a new access to enantioenriched CF3-containing building blocks.

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Iridium diamine catalyst for the asymmetric transfer hydrogenation of ketones

A simple and very efficient chiral aqua iridium(III) diamine complex leads to excellent enantioselectivities in the asymmetric transfer hydrogenation of various alpha-cyano and alpha-nitro ketones. The catalyst provides the ortho-substituted aromatic alcohols with especially high ee values. The diamine ligands can be used directly as chiral ligands; conversion into the corresponding sulfamide is not necessary.

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