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We report here the straightforward synthesis of the first series of enantiomerically pure azapyridinomacrocycles N-oxides containing a cyclohexyl chiral moiety. These compounds were readily obtained in good overall yields by a convergent synthesis using natural amino acids as starting building blocks and macrocyclisation as the key step. This method is rapid, efficient and suitable for the introduction of various substituents at the macrocyclic skeleton. Finally, the compounds were tested as organocatalysts for the enantioselective allylation of p-nitrobenzaldehyde with allyltrichlorosilane.

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

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The configurations and conformations of cis- and trans- 1,2-di (thio)acetamidocyclohexane and their N,N?-dimethyl derivatives have been studied by 1H and 13C NMR spectroscopy, using chemical shifts and coupling constants, difference NOE 1H NMR spectra and 2D 1H-13C NMR correlation spectra. For the trans compounds, the Z,Z configuration of the (thio)amide groups with equatorial (thio)acetamido groups was found to be strongly preferred. For the cis compounds, E,Z configurations of the (thio)amide groups with axial E and equatorial Z groups were found to be preferred. Empirical force-field calculations with the MM2(91) force field led to predictions for the most stable configurations and conformations, mostly in very good agreement with those obtained by NMR spectroscopy. CD spectra recorded for the trans-(R,R)-N-methyl compounds in acetonitrile solution agreed well with those calculated on the basis of geometries from force-field calculations. The CD spectra calculated for the trans-(R,R)-NH- compounds and for the cis-monothio compounds showed poor agreement with the experimental spectra. Acta Chemica Scandinavica 1996.

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Metal catalyst and ligand design,
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Peptide nucleic acid (PNA) is an achiral nucleic acid mimic with a backbone consisting of partly flexible aminoethyl glycine units. By replacing the aminoethyl portion of the backbone by an amino cyclohexyl moiety, either in the (S,S) or the (R,R) configuration, we have synthesized conformationally constrained PNA residues PNA oligomers containing (S.S)-cyclohexyl residues were able to form hybrid complexes with DNA or RNA, with little effect on the thermal stability (DeltaT(m) = ±1C per (S.S) unit, depending on their number and the sequence). In contrast, incorporation of the (R.R) isomer- resulted in a drastic decrease in the stability of tile PNA DNA (or RNA) complex (DeltaT(m)= 8C per (R,R) unit). In PNA PNA duplexes, however, the (R,R)- and (S,S)-cyclohexyl residues only exerted a minor effect on the stability, and the complexes formed with the two isomers are of opposite handedness, as evidenced from circular dichroism spectroscopy. In some cases the introduction era single (S,S) residue in a PNA 15-mer improves its sequence specificity for DNA or RNA. From the thermal stabilities and molecular modeling based on the solution structure of a PNA DNA duplex determined by N MR techniques, we conclude that the right-handed helix can accommodate the (S,S) isomer more easily than the (R,R) isomer. Thermodynamic measurements of DeltaH and AS upon PNA DNA duplex formation show that the introduction of an (S,S)-cyclohexyl unit in the PNA does indeed decrease the entropy loss, indicating a more conformationally constrained structure. However, the more favorable entropic contribution is balanced by a reduced enthalpic gain, indicating that the structure constrained by the cyclohexyl group is not so well suited for DNA hybridization.

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

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The new chiral ligands (S,S)-N,N?-bis[o-(diphenylphosphino)benzylidene]1,2-diiminocyclohexane, [(S,S)-1] and (S,S)-N,N?-bis[o-diphenylphosphino]benzyl-1,2-diaminocyclohexane, [(S,S)-2] have been prepared. The interaction of [(S,S)-1] and [(S,S)-2] with [Rh(COD)Cl]2 afforded the corresponding cationic rhodium complexes [(S,S)-3][X] and [(S,S)-4][X] (X=PF6-, BF4- or ClO4-), respectively. [(S,S)-1], [(S,S)-2], [(S,S)-3][X] and [(S,S)-4][X] have been fully characterized by elemental analyses and spectroscopic methods. These chiral cationic rhodium complexes serve as catalytst precursors for the asymmetric transfer hydrogenation of acetophenone derivatives in 2-propanol and [(S,S)-4][PF6] acts as an excellent catalyst in the reduction of m-chloroacetophenone, giving the corresponding optical alcohols in 99% yield and up to 94% ee.

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

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A Schiff base macrocycle having rhomboidal shape was synthesized through [2+2] cyclocondensation reaction between 4,4′-diformyl triphenylamine with (R,R)-1,2-diaminocyclohexane. The macrocyle structure was unambiguously proved by electrospray ionization mass spectrometry (ESI-MS), FTIR and 1H-NMR spectroscopy. The change of macrocycle’s conformation in solution was observed by 1H-NMR and UV spectroscopy. Reduction of rhombimine led to a rhombamine macrocycle.

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

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Herein we report the design and successful catalytic application of modified Trost-ligands in asymmetric allylic alkylation (AAA) reactions. A small set of carbamate-monophosphine P,O-ligands has been prepared in a straightforward two-step synthetic procedure. After optimization of the reaction conditions, high catalytic activities and excellent enantioselectivity up to >99% have been attained.

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

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Reaction of 4-tert-butyl-2,6-diformylphenol with (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane in the presence of 1 equivalent of Zn 2+ ions leads to selective formation of a chiral 2+2 macrocycle. Application of 0.5 equivalent of Zn2+ ions under the same conditions leads to selective formation of a chiral 3+3 macrocycle, which forms a cavitand-shaped trinuclear double-decker complex with Zn(ii).

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

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The synthesis of biaryl and terphenyl dicarboxaldehydes using Suzuki coupling methodology and their macrocyclisation reactions with 1R,2R-diaminocyclohexane yielding novel polyimine macrocycles derived from the [2+2] and [3+3] cyclocondensation reactions is presented. The ratio of products was found to depend on the overall geometry of the dicarboxaldehydes.

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Metal catalyst and ligand design,
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Porous organic cages are a class of adsorbents that have shown promise for a variety of applications. The octahedral cyclohexane-functionalised imine-based cage, commonly referred to as CC3, is perhaps most recognisable in this regard. However, most gas adsorption studies concerning this cage have focused on chromatographic or noble gas separations. Here, we examine this cage for the adsorptive separation of a wide variety of small molecules, including acetylene, ethylene, ethane, methane, and others. The internal surface of the cage is an optimal binding environment for gaseous substrates and as such the material displays adsorption enthalpies of ?15 to ?35 kJ/mol, depending on adsorbate. These values are particularly high for an adsorbent lacking coordinatively unsaturated metal sites and are likely a result of optimal cage geometry, which can be inferred from its isostructural nature to one of the pores in a well-known metal-organic framework, HKUST-1. Given this and the soluble nature of this cage, we additionally report optimisation of the high-pressure methane storage properties of this cage by tuning its density.

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

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Stable photoactive organogels were successfully prepared by a two-step sequence involving: 1) formation of thermoreversible organogels by use of a combination of low-molecular-weight organogelators (LMOGs) and Zn II-phthalocyanine (ZnII-Pc) moieties containing complementary organogelator structures, and 2) strength enhancement of the gels by in situ cross-linking with the aid of CuI-catalysed azidealkyne [3+2] cycloadditions (CuAACs). The optimum click reaction was carried out between a flexible C6 aliphatic diazide and a suitable diaIkyne (molar ratio 1:1) added in a low proportion relative to the organogelator system [LMOG+ZnIIPc]. The diaIkyne unit was incorporated into a molecule resembling the LMOGs structure in such a way that it could also participate in the self-assembly of [LMOG+ZnIIPc]. The significant compatibility of the multicomponent photoactive organogels towards this strengthening through CuAACs allowed their sol-to-gel transition temperatures (Tgel) to be enhanced by up to 15C. The Tgel values estimated by the “inverse flow method” were in good agreement with the values obtained by differential scanning calorimetry (DSC). Rheological measurements confirmed the viscoelastic, rigid, and brittle natures of all Pc-containing gels. Transmission and scanning electron microscopy (TEM, SEM) and atomic force microscopy (AFM) revealed the fibrilar nature of the gels and the morphological changes upon cross-linking by CuAAC. Emission of a red luminescence from the dry nanoscale fibrous structure – due to the self-assembly of the Pc-containing compounds in the organogel fibres – was directly observed by confocal laser scanning microscopy (CLSM). The optical properties were studied by UV/Vis and fluorescence spectroscopy. Fluorescence, Fourier-transform infrared (FTIR) and circular dichroism (Cd) measurements were also carried out to complete the physicochemical characterization of selected gels. As a proof of concept, two different organogelators (cholesterol- and diamide-based LMOGs) were successfully used to validate the general strategy.

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