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(Figure Presented) Copper or nickel? The depicted CuII salen complex, an active-site model of galactose oxidase (GO), is a localized radical in the solid state with a quinoid distribution of bond lengths in one ring. While the ligandradical structure is not metal-dependent, the composition of the radical SOMO is. This feature may explain the much lower reactivity of the Ni complex and nature’s preference for a CuII center in CO.

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Metal catalyst and ligand design,
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The synthesis of two 2-formylquinolines is reported via the Skraup method followed by SeO2 oxidation. Each aldehyde is condensed with (1R,2R)-diaminocyclohexane and (R)-BINAM, yielding four enantiomerically-pure bis(imine-quinoline) ligands. The neutral ligands are reacted with ZnCl 2 to give complexes with bis(bidentate) coordination of ZnCl 2 units. X-Ray structural characterization of three complexes shows them to have a single-stranded helical motif, with M helicity, except in one case where a 1: 1 mixture of M and P helices is seen. The ligands and complexes are further characterized spectroscopically by solution 1H and 13C NMR, UV-vis and ECD. The Royal Society of Chemistry.

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Aliskiren is the first-in-class orally active direct renin inhibitor. It was approved in 2007 for the treatment of hypertension. We have designed a new strategy for the convergent synthesis of aliskiren that involves a catalytic stereoselective nitroaldol reaction as the key step. A new enantiopure nitroalkane (synthon A1), prepared in only three steps from a commercially available enantiopure 2-(arylmethyl)-3-methyl butanol derivative, was successfully used in a copper-catalysed Henry reaction to give a nitrolactone intermediate in which the correct configuration for the final product was established at all four stereocentres. Nitro-group reduction, Boc-protection of the resulting amine, aminolysis of the lactone with 3-amino-2,2-dimethylpropionamide, and finally Boc-deprotection led to the enantiopure renin inhibitor aliskiren.

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[PdBr(chzn)2]Br2 with a halogen bridged 1-D structure forms a mixed-valence structure and contains a small amount of paramagnetic Pd3+ sites which were reported to migrate along the chain by forming neutral solitons. In this study, we prepared highly pure crystals by the electrochemical oxidation technique and measured electric conductivity, spin susceptibility and 1H NMR relaxation. Obtained results were compared with the data of crystals prepared by the previous Br2 gas diffusion method.

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Metal catalyst and ligand design,
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A diastereodivergent catalytic asymmetric Michael addition of 2-oxindoles to alpha,beta-unsaturated ketones has been successfully developed with two complementary chiral diamine catalysts, affording chiral 3,3-disubstituted oxindoles with two adjacent chiral centers. Diastereodivergence has been realized through modifying substrates and utilizing different catalysts. Either anti-or syn-configured products possessing vicinal quaternary and tertiary stereogenic centers were produced with high enantioselectivities.

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MRI contrast agents providing very high relaxivity values can be obtained through the attachment of multiple gadolinium(III) complexes to the interior surfaces of genome-free viral capsids. In previous studies, the contrast enhancement was predicted to depend on the rigidity of the linker attaching the MRI agents to the protein surface. To test this hypothesis, a new set of Gd-hydroxypyridonate based MRI agents was prepared and attached to genetically introduced cysteine residues through flexible and rigid linkers. Greater contrast enhancements were seen for MRI agents that were attached via rigid linkers, validating the design concept and outlining a path for future improvements of nanoscale MRI contrast agents.

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Metal catalyst and ligand design,
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An unprecedented enantioselective Michael addition of various ketones to maleimides catalyzed by a simple bifunctional primary amine, monosulfonyl DPEN salt, is reported and provides the desired adducts in good to excellent yields (up to 99%) with excellent enantioselectivities (up to 99%).

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The chiral nonaazamacrocyclic amine L, which is a reduction product of the 3 + 3 Schiff base macrocycle, wraps around the lanthanide(III) ions to form enantiopure helical complexes. These Ce(III), Pr(III), Nd(III), Eu(III), Gd(III), Tb(III), Er(III), Yb(III) and Lu(III) complexes have been isolated in enantiopure form and have been characterized by spectroscopic methods. X-ray crystal structures of the Ln(III) complexes with L show that the thermodynamic product of the complexation of the RRRRRR-isomer of the macrocycle is the (M)-helical complex in the case of Ce(III), Pr(III), Nd(III) and Eu(III). In contrast, the (P)-helical complex is the thermodynamic product in the case of Yb(III) and Lu(III). The NMR and CD spectra show that the (M)-helicity for the kinetic complexation product of the RRRRRR-isomer of the macrocycle is preferred for all investigated lanthanide(III) ions, while the preferred helicity of the thermodynamic product is (M) for the early lanthanide(III) ions and (P) for the late lanthanide(III) ions. In the case of the late lanthanide(III) ions, a slow inversion of helicity between the kinetic (M)-helical product and the thermodynamic (P)-helical product is observed in solution. For Er(III), Yb(III) and Lu(III) both forms have been isolated in pure form and characterized by NMR and CD. The analysis of 2D NMR spectra of the Lu(III) complex reveals the NOE correlations that prove that the helical structure is retained in solution. The NMR spectra also reveal large isotopic effect on the 1H NMR shifts of paramagnetic Ln(III) complexes, related to NH/ND exchange. Photophysical measurements show that LRRRRRR appears to favor an efficient 3??*-to-Ln energy transfer process taking place for Eu(III) and Tb(III), but these Eu(III)-and Tb(III)-containing complexes with LRRRRRR lead to small luminescent quantum yields due to an incomplete intersystem crossing (isc) transfer, a weak efficiency of the luminescence sensitization by the ligand, and/or efficient nonradiative deactivation processes. Circularly polarized luminescence on the MeOH solutions of Eu(III) and Tb(III) complexes confirms the presence of stable chiral emitting species and the observation of almost perfect mirror-image CPL spectra for these compounds with both enantiomeric forms of L.

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Metal catalyst and ligand design,
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The chiral bis-imine orthometallated [Pd(OAc)(C6H2-4,5-(OMe)2-2-CH-N-(1R,2R) -C6H10-N-CH-C6H3?,4?- (OMe)2-kappa-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-kappa-C,N,N)]), through C-H bond activation on only one of the aryl rings and N,N-coordination of the two iminiek N atoms. 2 reacts with an excess of LiC1 to give [Pd(C1)(L-kappa-C,N,N)] 3. The reaction of 3 with AgClO4 and neutral or amionic ligand L? (1:1:1 molar ratio) affords [Pd{L-kappa-C,N,N)(L?)](ClO4) (L?= PPh3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(1)(L-kappa-C,N,N)] 8. Complex 4a reacts with wet CDC13 giving [Pd(C6H2-4.5-(OMe)2 2-CH=N-(1R,2R) (C6H10 NH2-kappa-C,N,N) (PPh3)](ClO4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b-CH2Cl2 has been determined by X-ray diffraction methods. Cleavage of the Pd-N bond trans to the Caryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac-O,O?)(L-kappa-C,N)] 9 and [Pd(L-kappa-C,N)(dppen-P.P)](ClO4) 12, while classical N,N?-chelating ligands such as 1.10-phenantroline (phen) or 2.2?-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-kappa-C,N,N)(kappa1-N-phen)] (ClO4) 10 and [Pd(L-kappa-C,N,N)(kappa1-N-bipy)]C1O4) 11. Treatment of 1 with PtC12(DMSO)2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl2Pt[(NH2)2C6H10-H,N ?] 13a and [Pt{C1)(C6H2-4,5-(OMe)2 2-CH=N-(1R,2R)-C6H10-NH2-kappa-C,N,N)] 13b, while [Pt(C1)(L-kappa-C,N,N)] 14 can be obtained by reaction of [Pt(mu-C1)(eta3-2-Me-C3H4)]2 with 1 in refluxing CHC13. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity.

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Metal catalyst and ligand design,
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Three zinc(II) ions in combination with two units of enantiopure [3+3] triphenolic Schiff-base macrocycles 1, 2, 3, or 4 form cage-like chiral complexes. The formation of these complexes is accompanied by the enantioselective self-recognition of chiral macrocyclic units. The X-ray crystal structures of these trinuclear complexes show hollow metal-organic molecules. In some crystal forms, these barrel-shaped complexes are arranged in a window-to-window fashion, which results in the formation of 1D channels and a combination of both intrinsic and extrinsic porosity. The microporous nature of the [Zn312] complex is reflected in its N2, Ar, H2, and CO2 adsorption properties. The N2 and Ar adsorption isotherms show pressure-gating behavior, which is without precedent for any noncovalent porous material. A comparison of the structures of the [Zn312] and [Zn332] complexes with that of the free macrocycle H31 reveals a striking structural similarity. In H31, two macrocyclic units are stitched together by hydrogen bonds to form a cage very similar to that formed by two macrocyclic units stitched together by ZnII ions. This structural similarity is manifested also by the gas adsorption properties of the free H31 macrocycle. Recrystallization of [Zn312] in the presence of racemic 2-butanol resulted in the enantioselective binding of (S)-2-butanol inside the cage through the coordination to one of the ZnII ions.

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