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Starting from inexpensive L-(+)-tartaric acid, it was possible to resolve and obtain pure both enantiomers of trans-cyclohexane-1,2-diamine 1 and thence both enantiomers of BINOL 2, two of the most powerful, chiral inducing backbones in asymmetric catalysis. The modified method is very economic, not only due to an almost doubling of the overall yields of enantiomerically pure compounds (86% 1, 83% 2) but also due to the easy recovery of resolving agent 1 [66% (R,R)-1, 79% (S,S)-1] in the BINOL resolution. An improvement in the yield of the preparation of racemic BINOL is also recorded.

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The electronic structure of several cyclic, saturated and unsaturated amines and imines has been investigated by UV photoelectron spectroscopy (UPS). The analysis of spectra has been performed with DFT and OVGF calculations and comparison with the UPS spectra of related compounds. The extent and type of nitrogen lone pair interactions is discussed because nitrogen lone pairs are the most important functional groups present in these molecules. The magnitude of interactions was found to depend on the spatial orientation and rigidity of mutual positions of the lone pairs, rather than on their spatial distance.

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A nanocomposite was synthesized using carbon-coated Fe3O4 nanoparticle-decorated reduced graphene oxide as a convenient and efficient supporting material for grafting of a manganese?reduced Schiff base (salan) complex via covalent attachment. The nanocomposite was characterized using X-ray diffraction, Fourier transform infrared and diffuse reflectance UV?visible spectroscopies, inductively coupled plasma atomic emission spectrometry and scanning electron microscopy. It was evaluated as a catalyst for the aerobic epoxidation of olefins in acetonitrile in combination with a sacrificial co-reductant (isobutyraldehyde). The catalytic performance of the heterogeneous system of the Mn?salan complex is superior to that of the homogeneous one. The catalyst activity strongly depends on the reaction temperature and nature of the solvent. The epoxide yield increases with the nucleophilic character of the olefin. The nanocomposite performs well as an epoxidation catalyst for electron-rich and conjugated olefins. It can be recovered from the reaction medium by magnetic decantation and reused, maintaining good catalytic activity. Copyright

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Chiral Catalysts,
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9- and 10-membered macrolactones bearing benzo and diazine rings were obtained by chemoselective ozonolysis of dihydrofuran and pyran 1,4-diazaphenathrene derivatives. This is the first example of preparation of macrolactones by chemoselective ozonolysis of an enol double bond shared by aromatic and heterocyclic rings.

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Organogels are thermoreversible, viscoelastic (soft) materials consisting of low molecular weight compounds which self-assemble into fibers, often of micrometer lengths and nanometer diameters. The installation of terminal azide and alkyne functional groups on the end of a standard alkylamide-based organogelator was found to cause a modest disruption in the gelation properties of the molecule. Cross-linking of those groups by the copper(I)-catalyzed azide-alkyne cycloaddition reaction produced thermoreversible materials of substantially greater gelation temperatures and mechanical rigidity. These results highlight the ability of azides and alkynesparticipants in the most commonly used “click” reactionto function as innocuous precursors to meaningful covalent interactions in materials science. Copyright

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Mono- and diamides derivatives of 10,12-pentacosadiynoic acid (PCDA) were synthesized from condensation of PCDA with various aliphatic and aromatic diamines. Polydiacetylenes of the amidoPCDA derivatives were prepared by photopolymerization of their molecular assembly homogeneously dispersed in aqueous media. Thermochromic properties of the resulting polydiacetylene sol were studied by temperature variable UV-vis spectrometry along with photographic recording. The color transition temperatures and thermochromic reversibility of the polymers are varied depended on the number of amide groups and the structure of the aliphatic and aromatic linkers. The phenylenediamide and polymethylenediamide PCDA derivatives give polydiacetylenes with complete thermochromic reversibility, while the polydiacetylenes obtained from 1,2-cyclohexylene and glycolic chain diamide derivatives exhibited irreversible thermochromism, whereas the polymers attained from the aromatic monoamide analogues are partially reversible. The variation of the linkers also allows the color transition temperature of the polydiacetylene to be tuned in the range of 20 C to over 90 C. The results provide a fundamental idea about the factors affecting the thermochromic properties of polydiacetylenes toward the development of materials for universal thermal indicators.

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The ligand N-<2-amino-3-(p-isothiocyanatophenyl)propyl>-(+/-)trans-1,2-diaminocyclohexane-N,N’,N”-pentaacetic acid has been synthesized and linked to lgG and to monoclonal antibody B72.3 and labelled with 206Bi and 212Bi to demonstrate the in vivo stability of the label and its utility for 212Bi-radioimmunotherapy.

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Diesters (1 and 3) of (1S,2S) and (1R,2R)-cyclohexanediol and diamides (2 and 4) of (1S,2S) and (1R,2R)-diaminocyclohexane with p-hydroxycinnamic and exhibit intense bisignate circular dichroism spectra in CH3OH: 1 Deltaepsilon+55 (323 nm), -34 (287 nm); 2 Deltaepsilon+75 (318 nm), -55 (281 nm) and in (CH3)2SO: 1 Deltaepsilon+53 (328 nm), -33 (292 nm); 2 Deltaepsilon+65 (319 nm), -50 (280 nm). Added NaOH causes a bathochromic shift of ~50 nm in CH3OH and ~80-90 nm in (CH3)2SO.

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Two new catalysts are reported for the regioselective carbonylation of trans-disubstituted epoxides to cis-beta-lactones. The two catalysts display high and opposing selectivities, which generally are difficult to achieve for this class of epoxides. The resulting beta-lactones are well-defined precursors for a wide variety of aldol-type compounds. Altogether, carbonylation of disubstituted epoxides is established as a viable and economical entry into syn- and anti-aldol products.

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Chiral Salan ligands were found to wrap in a highly diastereoselective manner around zirconium leading to C2-symmetric complexes of predetermined chirality at the metal. These complexes led to active polymerization of higher olefins, their activity and isospecific induction depending on the nature of the phenolate substituents. Copyright

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Chiral Catalysts,
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