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Ni(NHC) Catalyzed Rearrangement of 1-Acyl-2-vinylcyclopropanes: Tackling a Mechanistic Puzzle by Combined Experimental and Computational Studies

The Ni(NHC) catalyzed rearrangement of 1-acyl-2-vinylcyclopropanes to the corresponding 4-acyl-cyclopent-1-enes is highly promising for the synthesis of keto-functionalized annelated bi- and tricyclic subunits of natural products. Therefore, we investigated the catalytic activity of Ni(NHC) complexes in the rearrangement of 1-acyl-2-vinylcyclopropanes with different ring sizes and substitution patterns. Surprising effects regarding substrate scope and stereoselectivity of the Ni(NHC) catalyzed vinylcyclopropane-cyclopentene rearrangement were observed. Only vinylcyclopropanes with 1-methyl, 1-phenyl, 1,2-dialkyl or 2-phenyl-substitution at the vinyl moiety could be rearranged successfully. Moreover, an endo-configuration on the cyclopropane ring was required for successful rearrangement. By treatment of the vinylcyclopropanes with Rh catalysts or Lewis acids, the involvement of Lewis acid catalysis could be ruled out. In order to understand these experimental results and to rationalize the reactivity of the Ni(NHC) complexes computational studies were performed, which provided insights into mechanistic details.

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Chiral Catalysts,
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Linear-selective hydroarylation of unactivated terminal and internal olefins with trifluoromethyl-substituted arenes

We report a series of hydroarylations of unactivated olefins with trifluoromethyl-substituted arenes that occur with high selectivity for the linear product without directing groups on the arene. We also show that hydroarylations occur with internal, acyclic olefins to yield linear alkylarene products. Experimental mechanistic data provide evidence for reversible formation of an alkylnickel -aryl intermediate and rate-determining reductive elimination to form the carbon – carbon bond. Labeling studies show that formation of terminal alkylarenes from internal alkenes occurs by initial establishment of an equilibrating mixture of alkene isomers, followed by addition of the arene to the terminal alkene. Computational (DFT) studies imply that the aryl C – H bond transfers to a coordinated alkene without oxidative addition and support the conclusion from experiment that reductive elimination is rate-determining and forms the anti-Markovnikov product. The reactions are inverse order in alpha-olefin; thus the catalytic reaction occurs, in part, because isomerization creates a low concentration of the reactant alpha-olefin.

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Chiral Catalysts,
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NHC-Cu-catalyzed protoboration of monosubstituted allenes. Ligand-controlled site selectivity, application to synthesis and mechanism

Two types of NHC-Cu complexes catalyze protoborations of terminal allenes to afford valuable 1,1- or trisubstituted vinylboron species with high site selectivity and stereoselectivity. The scope of the method, application to natural product synthesis, and mechanistic basis for the observed selectivity trends are presented.

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Chiral Catalysts,
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Application of 250285-32-6, Chemistry can be defined as the study of matter and the changes it undergoes. You¡¯ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride, molecular formula is C27H37ClN2. In a patent, introducing its new discovery.

Palladium-catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids

Readily available NHC-Pd(ii)-Mp complexes 2 showed efficient catalytic activity toward the Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the expected coupling products in good to high yields. It should be noted that this is the first example so far of the phosphine-free, NHC-Pd(ii) complexes catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids.

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Chiral Catalysts,
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POLY-N-HETEROCYCLIC CARBENE TRANSITION METAL COMPLEXES AND N-HETEROCYCLIC CARBENE TRANSITION METAL COMPLEXES FOR CARBON-SULFUR AND CARBON-OXYGEN COUPLING REACTIONS

Methods for carbon-sulfur (C S) or carbon-oxygen (C-O) coupling reactions are provided. The methods involve the use of a transition metal complex comprising a heterocyclic carbene ligand complexed with a transition metal. Transition metal complexes comprising a heterocyclic carbene ligand complexed with nickel are also provided. The nickel heterocylic carbene complexes may be used for C-S or C-O coupling reactions.

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Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn¡¯t involve a screen. 250285-32-6, C27H37ClN2. A document type is Article, introducing its new discovery., Quality Control of: 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride

Cyclometalated Palladium NHC Complexes Bearing PEG Chains for Suzuki-Miyaura Cross-Coupling in Water

We present the synthesis and characterization of four new polyethylene glycol (PEG) substituted palladium complexes bearing a cyclometalated 2-phenylimidazole ligand and an N-heterocyclic carbene (NHC) ligand. A solid-state structure reveals the chelating binding mode and the coiling of the PEG chain in the auxiliary ligand. The PEG substitution significantly increased the solubility of the complexes in several solvents, enabling the efficient Suzuki-Miyaura cross-coupling reaction of aryl chlorides in an aqueous medium. Under optimized reaction conditions, sterically demanding biphenyl compounds with up to three ortho substituents were accessible in good to excellent yields.

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Chiral Catalysts,
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In an article, published in an article, once mentioned the application of 250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride,molecular formula is C27H37ClN2, is a conventional compound. this article was the specific content is as follows.Quality Control of: 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride

N-heterocyclic carbene-catalyzed all carbon-[4+2] cyclocondensation of alpha,beta-unsaturated acyl chlorides with 3-alkylenyloxindoles

Although the NHC-catalyzed cyclization reactions have been well established for the synthesis of various heterocycles, the corresponding all carbon cyclization reaction for the synthesis of carbocycles is far less established. In this note, the NHC-catalyzed all carbon [4+2] cyclocondensation of alpha,beta-unsaturated acyl chlorides and 3-alkenyloxindoles was developed to give the corresponding spirocarbocyclic oxindoles in good yield with good to high diastereoselectivities. The NHC-catalyzed all carbon [4+2] cyclocondensation of alpha,beta-unsaturated acyl chlorides and 3-alkenyloxindoles was developed to give the corresponding spirocarboncyclic oxindoles in good yield with good to high diastereoselectivities. Copyright

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride, molecular formula is C27H37ClN2. In a Article£¬once mentioned of 250285-32-6, SDS of cas: 250285-32-6

Iron-catalyzed coupling of aryl sulfamates and aryl/vinyl tosylates with aryl grignards

The iron-catalyzed coupling of aryl sulfamates and tosylates with aryl Grignard reagents is reported for the first time. The methodology employs air-stable, low-cost FeF3¡¤3H2O and the N-heterocyclic carbene ligand IPr¡¤HCl as the preligand to form a long-lived catalyst upon treatment with aryl Grignards. The reaction provides a range of cross-coupled products in good-to-excellent yields. In contrast to previous reports with aryl chlorides, these reactions proceed with low levels of Grignard homocoupling regardless of the iron source.

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Chiral Catalysts,
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Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed C-N Bond Cleavage

A protocol for the nickel-catalyzed alkylation of amides was established. The use of alkylboranes as nucleophilic partners allowed the use of mild reaction conditions and compatibility of various functional groups with respect to both coupling partners. The catalytic alkylation proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.

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Chiral Catalysts,
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TWO-PACK TYPE EPOXY RESIN COMPOSITION FOR FIBER-REINFORCED COMPOSITE MATERIAL, AND FIBER-REINFORCED COMPOSITE MATERIAL

A task of the invention is to provide a two-component type epoxy resin composition that is excellent in the viscosity stability at low temperature (e.g., 40C) of an epoxy resin composition after the mixing preparation, and that retains low viscosity at the time of injection into reinforcing fiber and is excellent in impregnating property, and that controls resin flow due to the resin viscosity appropriately increasing after impregnation so that, for example, burrs on a molded product can be reduced, and that cures in a short time during molding, and that gives a fiber reinforced composite material high in the transparency of a cured product and excellent in molded product quality, and a fiber reinforced composite material made by using the two-component epoxy resin composition. The two-component type epoxy resin composition for a fiber reinforced composite material of the invention is a two-component type epoxy resin composition for a fiber reinforced composite material that includes the following components [A] to [C], wherein the content of the component [C] is 6 to 25 mass parts relative to 100 mass parts of the component [A]. The fiber reinforced composite material of the invention is a fiber reinforced composite material made by combining and curing the two-component type epoxy resin composition for the fiber reinforced composite material and a reinforcing fiber. [A]: an epoxy resin [B]: an acid anhydride [C]: a quaternary ammonium salt or a quaternary phosphonium halide or an imidazolium salt

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Chiral Catalysts,
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