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The stereoselective hetero Diels-Alder reaction between ethyl glyoxylate and cyclohexadiene catalyzed by [Cu(ii)t-Bu-(box)](OTf)2 was investigated. The reaction was performed step-by-step and the geometry of the Cu(ii) complexes formed in the course of the catalysis was analysed by EPR spectroscopy, advanced pulsed EPR methods (ENDOR, and HYSCORE) and DFT calculations. Our results show that one triflate counterion is directly coordinated to Cu(ii) during the catalytic process (axial position). This leads to penta-coordinated Cu(ii) complexes. Solvent molecules are able to alter the geometry of the Cu(ii) complexes although their coordination is weak. These findings provide an explanation for the solvent and counterion effects observed in many catalytic reactions.

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

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Application of 131833-93-7, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.131833-93-7, Name is (4S,4’S)-2,2′-(Propane-2,2-diyl)bis(4-(tert-butyl)-4,5-dihydrooxazole), molecular formula is C17H30N2O2. In a Article,once mentioned of 131833-93-7

Organofluorine compounds are found in several important classes of chemicals, such as pharmaceuticals, agrochemicals, and functional materials. Chemists have been immensely interested in the development of methodologies for expeditious access to fluorine containing building blocks. In this study, we report a new method for the catalytic asymmetric synthesis of CF3-substituted tertiary propargylic alcohols with two contiguous stereogenic centers via the direct aldol reaction of an alpha-N3 amide to trifluoromethyl ketones. The key to the success of this method is the identification of a catalyst comprising Cu(ii)/chiral hydroxamic acid to promote the desired aldol reaction, constructing a tetrasubstituted carbon in a highly stereoselective fashion. Despite substantial prior advances in asymmetric catalysis, this class of catalysts has not been utilized for the formation of carbon-carbon bond-forming reactions. Our mechanistic study sheds light on the unique profile of this catalytic system, where the Cu(ii) complex plays a bifunctional role of serving as a Lewis acid and a Br°nsted base. Furthermore, the densely functionalized aldol adducts undergo chemoselective transformations, affording a series of fluorine containing chiral building blocks with widespread application.

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

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The copper-catalyzed H-F insertion into alpha-diazocarbonyl compounds is described using potassium fluoride (KF) and hexafluoroisopropanol. Access to complex alpha-fluorocarbonyl derivatives is achieved under mild conditions, and the method is readily adapted to radiofluorination with [18F]KF. This late-stage strategy provides an attractive route to 18F-labeled biomolecules.

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

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Mass spectrometric screening of enantioselective Diels-Alder reactions

(Chemical Equation Presented) A rapid cat. scan: Mass spectrometric monitoring of reaction intermediates of the retro-Diels-Alder reaction has allowed the rapid screening of catalysts for enantioselective Diels-Alder reactions (see scheme). Copper catalysts as well as metal-free organocatalysts were tested. A protocol for the simultaneous screening of catalyst mixtures has also been developed, which offers new possibilities for high-throughput catalyst development.

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

Final Thoughts on Chemistry for (4S,4’S)-2,2′-(Propane-2,2-diyl)bis(4-(tert-butyl)-4,5-dihydrooxazole)

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Concise total synthesis of albaflavenone utilizing sequential intramolecular aldol condensation: Determination of absolute configuration

The first total synthesis of albaflavenone, a novel antibiotic sesquiterpene, has been accomplished via the concise construction of its zizaene skeleton utilizing sequential intramolecular aldol condensation followed by chemo- and diastereoselective reduction of the conjugated carbon-carbon double bond. This synthetic work was completed in nine steps from 2-cyclopenten-1-one as a starting material without the use of protecting groups and with high stereocontrol. In addition, the absolute configuration of naturally occurring albaflavenone was determined to be 1R,2S and 8S.

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

More research is needed about (4S,4’S)-2,2′-(Propane-2,2-diyl)bis(4-(tert-butyl)-4,5-dihydrooxazole)

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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, 131833-93-7, molcular formula is C17H30N2O2, introducing its new discovery. Formula: C17H30N2O2

Chiral bis(oxazoline)copper(II) complexes as lewis acid catalysts for the enantioselective Diels-Alder reaction

Bis(oxazoline)copper(II) complexes are highly enantioselective catalysts in Diels-Alder reactions involving bidentate dienophiles. Cationic [Cu((S,S)- t-Bu-box)]X2 complexes with different counterions have been used as catalysts, revealing a profound influence of the counterion on the rate and stereoselectivity of the catalyst. A square-planar catalyst-substrate complex is proposed to account for the high diastereo- and enantioselectivities observed. Three bis(oxazoline)-Cu(II) X-ray structures have been obtained that support this model. Double-stereodifferentiating experiments, performed employing chiral dienophiles, afforded results that are fully consistent with the proposed square-planar transition-state assemblage. In addition to imide- based substrates, alpha,beta-unsaturated thiazolidine-2-thiones have been introduced as a new class of dienophiles with enhanced reactivity. Kinetics experiments were performed to quantify the role that product inhibition plays in the course of the reaction. Rate and equilibrium binding constants of various catalyst inhibitors were also derived from the kinetic analysis. A comparative study was undertaken to elucidate the differences between the bis(oxazoline)-Cu(II) catalyst and the bis(oxazoline) catalysts derived from Fe(III), Mg(II), and Zn(II). Catalyst performance was found to be a function of a subtle relationship between bis(oxazoline) structure and transition metal.

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Reference£º
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, 131833-93-7, molcular formula is C17H30N2O2, introducing its new discovery. Recommanded Product: (4S,4’S)-2,2′-(Propane-2,2-diyl)bis(4-(tert-butyl)-4,5-dihydrooxazole)

Desymmetrization by Asymmetric Copper-Catalyzed Intramolecular C-H Insertion Reactions of alpha-Diazo-beta-oxosulfones

Effective desymmetrization in copper-catalyzed intramolecular C-H insertion reactions of alpha-diazo-beta-oxosulfones in the formation of fused thiopyran dioxides is described for the first time. The use of a copper-bis(oxazoline)-NaBARF catalyst complex system leads to formation of the major thiopyran dioxide stereoisomer with up to 98:2 dr and up to 98% ee. The effect of varying the bis(oxazoline) ligand, copper salt, and site of C-H insertion on both diastereo- and enantioselectivities of these intramolecular C-H insertion reactions has been investigated. Similarly, desymmetrization in the formation of a fused cyclopentanone proceeds with up to 64% ee. These results represent the highest enantioselectivity reported to date in a copper-mediated desymmetrization through C-H insertion.

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

Awesome Chemistry Experiments For (4S,4’S)-2,2′-(Propane-2,2-diyl)bis(4-(tert-butyl)-4,5-dihydrooxazole)

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Iron-catalyzed hydrogenation for the in situ regeneration of an NAD(P)H model: Biomimetic reduction of alpha-Keto-/alpha-iminoesters

Two irons for a smoother finish: An NAD(P)H model was regenerated readily in situ by iron-catalyzed reduction with molecular hydrogen. The subsequent biomimetic reduction of alpha-keto-/ alpha-iminoesters proceeded smoothly in the presence of an iron-based Lewis acid (LA) to provide alpha-hydroxyesters and amino acid esters in good to excellent yields (see scheme; NAD(P) +=nicotinamide adenine dinucleotide (phosphate), TM=transition metal). Copyright

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

The important role of (4S,4’S)-2,2′-(Propane-2,2-diyl)bis(4-(tert-butyl)-4,5-dihydrooxazole)

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Diastereoselective silylene transfer reactions to chiral enantiopure alkenes: Effects of ligand size and substrate bias

Silylenes are useful reactive intermediates for the stereoselective construction of compounds containing carbon-silicon bonds. Despite their synthetic utility, the development of either an enantioselective or diastereoselective metal-catalyzed silylene transfer reaction, in which ligands on the metal catalyst control stereoselectivity, has not been achieved. In this article, we report that the structure of the alkene is the most important for controlling stereoselectivity in these reactions. The stereochemical course of kinetically controlled silacyclopropanation reactions was not affected by the nature or chirality of the ligands on the metal. When silylene transfer reactions were reversible, however, products can be formed with a high degree of diastereoselectivity (90:10 d.r.).

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

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A unified stereodivergent strategy for prostaglandin and isoprostanoid synthesis

Acetoxyfulvene surrended to asymmetric Diels-Alder cycloaddition, paving the way to the development of a unified strategy for the stereodivergent synthesis of both prostaglandins and isoprostanoids. In fact, the cycloadduct was subsequently converted to a common intermediate, which through two different stereoselective pathways afforded the two lactones 1 and 2, which are key building blocks in the synthesis of prostaglandins and isoprostanoids, respectively.

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