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Tetrahydro-1,4-epoxynaphthalene-1-carboxylic acid (THENA), was applied as a chiral derivatizing agent to resolve 7,7′-disubstituted 1,1′-bi-2-naphthol derivatives. This process is very efficient and could potentially be used as a preliminary tool to assign the absolute configuration of substituted 1,1′-bi-2-naphthols by means of a simple TLC.

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

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Directed helicity control of a polyacetylene dynamic helix was achieved by hybridization with a rotaxane skeleton placed on the side chain. Rotaxane-tethering phenylacetylene monomers were synthesized in good yields by the ester end-capping of pseudorotaxanes that consisted of optically active crown ethers and sec-ammonium salts with an ethynyl benzoic acid. The monomers were polymerized with [{RhCl(nbd)}2] (nbd=norbornadiene) to give the corresponding polyacetylenes in high yields. Polymers with optically active wheel components that are far from the main chain show no Cotton effect, thereby indicating the formation of racemic helices. Our proposal that N-acylative neutralization of the sec-ammonium moieties of the side-chain rotaxane moieties enables asymmetric induction of a one-handed helix as the wheel components approach the main chain is strongly supported by observation of the Cotton effect around the main-chain absorption region. A polyacetylene with a side-chain rotaxane that has a shorter axle component shows a Cotton effect despite the ammonium structure of the side-chain rotaxane moiety, thereby suggesting the importance of proximity between the wheel and the main chain for the formation of a one-handed helix. Through-space chirality induction in the present systems proved to be as powerful as through-bond chirality induction for formation of a one-handed helix, as demonstrated in an experiment using non-rotaxane-based polyacetylene that had an optically active binaphthyl group. The present protocol for controlling the helical structure of polyacetylene therefore provides the basis for the rational design of one-handed helical polyacetylenes.

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

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Formation of the cholesteric phase in aqueous lyotropic liquid crystals doped with cellulose derivatives has been studied utilizing hot stage polarized microscopy. Three ionic surfactants-sodium decyl sulfate, cesium pentadecafluorooctanoate, and myristyltrimethylammonium bromide-were employed to obtain anionic or cationic lyonematics. After addition of chiral polymers (at polymer concentration ~0.05-0.750 wt %) the samples were sealed in flat glass capillaries, and a magnetic field was applied to enhance the homogeneous orientation and formation of the fingerprint texture. Out of seven various cellulosic derivatives (five nonionic, one cationic, and one anionic), nonionic hydroxypropyl cellulose was the only compound that induced the cholesteric phase. The effective helical twisting power (HTP) of hydroxypropyl cellulose is 3-4 times higher in anionic lyonematics than in cationics. In both cationic and anionic media, the HTP decreases with an increase in the molecular weight of the chiral polymer. This behavior can be attributed to two factors: (i) inhomogeneous distribution of chiral centers (formation of polymer bound chiral micelle clusters) and (ii) the finite character of intermicellar chiral distortion forces. The pitch of the polymer-doped cationic chiral lyonematic decreases as the temperature rises, indicating a closer packing along the helical axis with an increase in the thermal motion of the system.

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

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The rhodium-catalyzed enantioselective desymmetrization of symmetric gamma,delta-unsaturated amides via carbonyl-directed catalytic asymmetric hydroboration (directed CAHB) affords chiral secondary organoboronates with up to 98% ee. The chiral gamma-borylated products undergo palladium-catalyzed Suzuki-Miyaura cross-coupling via the trifluoroborate salt with stereoretention.

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

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Several chiral BINADCo(III)X (BINAD = Bis(1,1?-2-hydroxy-2?-alkoxy-3-naphthylidene)-1,2-cyclohexanediamine, X = OAc, CF3CO2, CCl3CO2, OTs, p-NO2PhCO2) complexes were synthesized and used to catalyze the asymmetric cycloaddition of carbon dioxide with epoxides under mild condition to afford chiral cyclic carbonates. The best catalyst of (S,S,S,S)-BINADCo(III)(OAc) 9b and phenyltrimethylammonium tribromide (PTAT) can provide propylene carbonate with the highest ee being 95% at -20 C.

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

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A simple chromatography-free high-yielding synthesis of the hexane-soluble enantiopure 6,6?-di-tert-butyl-1,1?-binaphthalene-2,2?-diol 3 (6,6?-di-tert-butyl BINOL) using Friedel-Crafts reaction on 1,1?-binaphthalene-2,2?-diol 1 (BINOL) is described. The enantiomeric purity was fully maintained in the reaction. Compound 3 has been used as an entry point for the convenient chromatography-free synthesis of 3,3?,6,6?-tetra-tert-butyl BINOL 4 and 3,3?-dibromo-6,6?-di-tert-butyl BINOL 5. A straightforward route to enantiopure bisphosphites [(6,6?-R2C20H10O2)P]2[O2C20H10-6,6?-R2] [R = H 15, t-Bu 16] by simply reacting phosphorochloridite (6,6?-R2C20H10O2)PCl [R = H 20, t-Bu 6] with metallic sodium is highlighted. The identity of 15 and 16 as their selenium-oxidized products 17 and 18 (at phosphorus center) is confirmed by X-ray crystallography (17 in the enantiopure form and 18 as racemate). Various enantiopure phosphoramidites of the modified BINOL have been synthesized. It is established that even when the phosphoramidites derived from the unsusbstituted BINOL 1 fail to give an appreciable optical induction in the asymmetric reduction of acetophenone/phenacyl chloride, those derived from 3 do induce moderate chiral induction (up to 30% ee in the case for acetophenone and 43% ee in the case of phenacyl chloride), thus leaving scope for further improvement in ee for related reactions.

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

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We report a highly selective asymmetric ring-closing ene reaction catalysed by aluminum complexes with chiral BINOL. This reaction yields optically active 6-membered cyclized alcohols from unsaturated aldehydes, with good diastereo- and enantioselectivities. Asymmetric amplification of this reaction was investigated by varying the ee of the BINOL employed in the catalyst.

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

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A facile enantioselective 1,4-addition of TMSCN to aromatic enones has been developed using chiral sodium phosphate. Thus, in the presence of 20 mol% of sodium salt generated in situ from (R)-3,3?-di(1-adamantyl)-1,1?- binaphthyl-2,2?-diylphosphoric acid and NaOH, beta-cyano ketones were obtained in high yield (86-96%) and up to 72% ee within three hours at 80 C in toluene.

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

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 18531-94-7, molcular formula is C20H14O2, introducing its new discovery. name: (R)-[1,1′-Binaphthalene]-2,2′-diol

The present invention provides a chiral three-valent metal complex, said chiral three-valent metal complex is composed of two carbon – gold covalent bond, a covalent bond oxygen – nitrogen and a gold – gold coordination bond form, provided with a hand natural dinaphthol and oxazoline ligand skeleton, or with hand natural dinaphthol and ortho-substituted pyridine ligand framework, said chiral three-valent metal complex having the following general formula I or general formula II compound, and the […] I or the formula II of the racemate and optically active isomers, (by machine translation)

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

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A polyelectrolyte multilayer (PEM) coating consisting of the polypeptide, poly(L-lysine) hydrobromide, poly(L-lysine) and the polymeric dipeptide surfactant, poly(sodium undecanoyl-L-leutcyl-alaninate), poly(L-SULA), is investigated as a new medium for the separation of chiral analytes in open-tubular capillary electrochromatography (OT-CEC). In this approach, a stable PEM is constructed in situ by alternative rinses of the cationic polymer poly(L-lysine) and the anionic polymer poly(L-SULA). In previous studies, the PEM coating has been constructed by use of the cationic polyelectrolyte poly (diallydimethylammonium chloride), PDADMAC. In this study, we investigate the use of a biopolymer as the cationic polyelectrolyte. The results reported here indicate an increase in selectivity and resolution when poly(L-lysine) is used as the cationic polymer in place of PDADMAC. To evaluate the chromatographic performance of the PEM coating as a chiral stationary phase, the separation of the beta-blockers, labetalol and sotalol, and the binaphthyl derivatives, 1,1?-bi-2-naphthyl-2,2?-dihydrogen phosphate, 1,1?-bi-2- naphthol, and 1,1-binaphthyl-2,2?-diamine, are investigated. In addition, the effect of varying the amino acid order of the polymeric dipeptide surfactant on resolution is investigated. The number of bilayers also significantly influences the separation efficiency and resolution of enantiomers. The run-to-run and capillary-to-capillary reproducibilities are evaluated by calculating the relative standard deviations (RSDs) of the electroosmotic flow. These RSD values were found to be less than 1%. The coating is also stable and allows more than 290 runs to be performed in the same capillary. In addition, coupling of this chiral OT-CEC column with mass spectrometry is investigated.

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