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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, Application In Synthesis of (R)-[1,1′-Binaphthalene]-2,2′-diol, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 18531-94-7, Name is (R)-[1,1′-Binaphthalene]-2,2′-diol, molecular formula is C20H14O2. In a Article, authors is Tamai, Yasufumi£¬once mentioned of 18531-94-7

A New Approach to Remote Asymmetric Induction in the Diastereoselective Reduction of gamma-Keto Esters by Use of a Chiral Podand as Chiral Auxiliary

An efficient 1,7-asymmetric induction was achieved with up to 82percent diastereoisomeric excess (d.e.) in the diastereoselective reduction of the gamma-keto ester 4 and o-acetylbenzoate 6 using a chiral podand 2 as a chiral auxiliary.

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

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Asymmetric catalytic carbon-carbon bond formations in a fluorous biphasic system based on perfluoroalkyl-BINOLs

Optically active 1,1?-binaphthols (BINOLS) substituted at the 4,4?; 6,6? and 4,4?,6,6? positions with perfluoroalkyl groups have been synthesized. Asymmetric diethylzinc and triethyl aluminum addition to aryl aldehydes in a fluorous biphasic system catalyzed by these perfluoroalkyl-BINOL-titanium complexes have been accomplished with good enantiomeric excess obtained.

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

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Reductive ring opening of dihydrodibenzothiepine and dihydrodinaphtho- oxepine and -thiepine

The 4,4?di-tert-butylbiphenyl (DTBB)-catalysed lithiation of dihydrodibenzothiepine (1) at -78C for 30 min followed by reaction with a carbonyl compound [tBuCHO, Ph(CH2)2CHO, PhCHO, (n-C5H11)2CO, (CH2)5CO, (CH2)7CO, (-)-menthone] at the same temperature leads, after hydrolysis with 3 M hydrochloric acid, to sulphanyl alcohols 2. If after addition of a carbonyl compound as the first electrophile [Me2CO, (CH2)5CO, (-)-menthone], the resulting dianion of type II is allowed to react at room temperature for 30 min, a second lithiation takes place to give an intermediate of type III, which by reaction with a second electrophile [Me2CO, Et2CO, (CH2) 5CO, ClCO2Et], yields, after hydrolysis, difunctionalised byphenyls 4. The cyclisation of the sulphanyl alcohol 2c under acidic conditions yields the eight-membered sulphur containing heterocycle 3. The lithiation of dihydrodinaphthoheteroepines 7 and 10 with 2.2 equiv of lithium naphthalenide in THF at -78C followed by reaction with different electrophiles [H 2O, D2O, tBuCHO, Me2CO, Et 2CO, (CH2)4CO, (CH2)5CO] at the same temperature leads, after hydrolysis, to unsymmetrically 2,2?-disubstituted binaphthyls 9 and 12, respectively. When the lithiation is performed with an excess of lithium in the presence of a catalytic amount of DTBB (10% molar), a double reductive cleavage takes place to give the dianionic intermediate VII, which by reaction with different electrophiles [H 2O, Me2CO, Et2CO, (CH2) 4CO, (CH2)5CO], followed by hydrolysis with water, yields symmetrically 2,2?-disubstituted binaphthyls 8 and 11. In the case of starting from (R)- or (S)-dihydrodinaphthoheteroepines 7 and 10, these methodologies allow us to prepare enantiomerically pure compounds 8, 11 and 12.

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

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Simple chiral derivatization protocols for 1H NMR and 19F NMR spectroscopic analysis of the enantiopurity of chiral diols

(Chemical Equation Presented) Two practically simple chiral derivatization protocols for determining the enantiopurity of chiral diols by 1H NMR and 19F NMR spectroscopic analysis are described, involving treatment of the diol with 2-formylphenylboronic acid and alpha-methyl-4- fluorobenzylamine, or its derivatization with 4-fluoro-2-formylphenylboronic acid and alpha-methyl-benzylamine. Both approaches afford mixtures of imino-boronate esters whose diastereomeric ratio may be measured by 1H NMR or 19F NMR spectroscopy, the value of which is an accurate reflection of the enantiopurity of the parent diol.

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

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Polyfunctional Imidazolium Aryloxide Betaine/Lewis Acid Catalysts as Tools for the Asymmetric Synthesis of Disfavored Diastereomers

Enzymes are Nature’s polyfunctional catalysts tailor-made for specific biochemical synthetic transformations, which often proceed with almost perfect stereocontrol. From a synthetic point of view, artificial catalysts usually offer the advantage of much broader substrate scopes, but stereocontrol is often inferior to that possible with natural enzymes. A particularly difficult synthetic task in asymmetric catalysis is to overwrite a pronounced preference for the formation of an inherently favored diastereomer; this requires a high level of stereocontrol. In this Article, the development of a novel artificial polyfunctional catalyst type is described, in which an imidazolium-aryloxide betaine moiety cooperates with a Lewis acidic metal center (here Cu(II)) within a chiral catalyst framework. This strategy permits for the first time a general, highly enantioselective access to the otherwise rare diastereomer in the direct 1,4-addition of various 1,3-dicarbonyl substrates to beta-substituted nitroolefins. The unique stereocontrol by the polyfunctional catalyst system is also demonstrated with the highly stereoselective formation of a third contiguous stereocenter making use of a diastereoselective nitronate protonation employing alpha,beta-disubstituted nitroolefin substrates. Asymmetric 1,4-additions of beta-ketoesters to alpha,beta-disubstituted nitroolefins have never been reported before in literature. Combined mechanistic investigations including detailed spectroscopic and density functional theory (DFT) studies suggest that the aryloxide acts as a base to form a Cu(II)-bound enolate, whereas the nitroolefin is activated by H-bonds to the imidazolium unit and the phenolic OH generated during the proton transfer. Detailed kinetic analyses (RPKA, VTNA) suggest that (a) the catalyst is stable during the catalytic reaction, (b) not inhibited by product and (c) the rate-limiting step is most likely the C-C bond formation in agreement with the DFT calculations of the catalytic cycle. The robust catalyst is readily synthesized and recyclable and could also be applied to a cascade cyclization.

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

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Synthesis and enantiomeric recognition ability of 22-crown-6 ethers derived from rosin acid and BINOL

Four novel chiral 22-crown-6 ethers 6a-b, 7a-b bearing hydroxyl side groups derived from rosin acid and BINOL were prepared in optically pure forms, and their enantiodiscriminating abilities towards protonated primary amines and amino acid methyl ester salts were examined by UV-vis titration methods. These receptors exhibited good chiral recognition towards the isomers (up to K D/KL = 6.02, DeltaDeltaG0 = 4.45 kJ mol-1) and showed different complementarity to various chiral guests.

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

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 18531-94-7, name is (R)-[1,1′-Binaphthalene]-2,2′-diol, introducing its new discovery. name: (R)-[1,1′-Binaphthalene]-2,2′-diol

Ortho-Acidic aromatic thiols as efficient catalysts of intramolecular Morita-Baylis-Hillman and Rauhut-Currier reactions

ortho-Mercaptobenzoic acid and ortho-mercaptophenols were discovered as efficient thiol catalysts of both the intramolecular Morita-Baylis-Hillman (MBH) and Rauhut-Currier (RC) reaction. High reaction rates were achieved under mildly basic, aqueous conditions. The unprecedented catalytic activity of these protic nucleophiles could originate from a Br¡ãnsted acid induced destabilization of intermediate thioethers and thus represent a unique mechanism of multifunctional Lewis base catalysis.

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

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 18531-94-7, name is (R)-[1,1′-Binaphthalene]-2,2′-diol, introducing its new discovery. Safety of (R)-[1,1′-Binaphthalene]-2,2′-diol

1,1?-binaphthalene-2,2?-diol as a chiral auxiliary. Diastereoselective alkylation of binaphthyl esters, complex-induced proximity effects in enolate formation, and one-step synthesis of an optically active beta-substituted ketone

Diastereoselective alkylation of enolates derived from (S)-naphthyl phenylacetate 1 with LDA in THF gave the S,S-isomer as a major product. The diastereoselectivity increased as the bulkiness of the alkylating agent was increased. The low diastereomeric excess (?70%) of methylation was markedly raised to 92% by the use of n-BuLi as a base due to the complex-induced proximity effect (CIPE) in enolate formation. This highly diastereoselective methylation was used to synthesize the clinically important anti-inflammatory drugs (S)-naproxen (60) and (S)-suprofen (68). The stereochemistry of ketene trimethylsilyl acetals generated from several phenylacetates was investigated to understand the origin of the diastereoselectivity in this alkylation. Methyl phenylacetate (46) predominantly gave a (Z)-enolate by kinetic deprotonation, while the (E)-enolate was predominantly obtained from phenyl phenylacetate (47). An optically active ketone (88) was synthesized from binaphthyl ester 84 by a one-pot procedure involving the 1,4-addition, followed by the 1,2-addition, of organometallics. The CIPE again played a crucial role in the high enantiomeric excess in this case.

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

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Thermally activated delayed fluorescence enantiomers for solution-processed circularly polarized electroluminescence

Circularly polarized organic light-emitting diodes (CP-OLEDs) with thermally activated delayed fluorescence (TADF) characteristics are receiving increasing interest, as they have shown improving efficiencies of circularly polarized electroluminescence (CPEL). Here, we developed a series of TADF enantiomers based on chiral binaphthalene, an acceptor (A) of cyanopyridine, and donors (D) of carbazoles in a chiral-A-D architecture. Good solubility, high luminescence yields, and excellent chiral stability with a photoluminescence dissymmetry factor (gPL) up to 5.8 ¡Á 10-4 were achieved. Efficient CP-OLEDs using these chiral TADF molecules as dopants were successfully fabricated, exhibiting high external quantum efficiencies (EQEs) up to 12.4% and opposite CPEL signals with gEL of 6 ¡Á 10-4/-8.6 ¡Á 10-4 in vacuum-deposited devices. More impressively, the solution-processed TADF CP-OLEDs result in much larger gEL values (3.5 ¡Á 10-3/-3.9 ¡Á 10-3) with EQEs up to 10.6%. This discovery is encouraging and instructive, which could stimulate the development of high-performance CP-OLEDs using chiral TADF molecules through solution-processing approaches.

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

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A homochiral microporous hydrogen-bonded organic framework for highly enantioselective separation of secondary alcohols

A homochiral microporous hydrogen-bonded organic framework (HOF-2) based on a BINOL derivative has been synthesized and structurally characterized to be a uninodal 6-connected {3355667} network. This new HOF exhibits not only a permanent porosity with the BET of 237.6 m 2 g-1 but also, more importantly, a highly enantioselective separation of chiral secondary alcohols with ee value up to 92% for 1-phenylethanol.

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