Kumada-Corriu Reactions Research Articles

Palladium-catalyzed C-H dimethylamination of 1-chloromethyl naphthalenes with N,N-dimethylformamide as the dimethyl amino source.

Palladium-catalyzed remote C-H dimethylamination of 1-chloromethylnaphthalenes using N,N-dimethylformamide as the dimethylamino source is described for the first time. The dimethylamination took place exclusively at the 4-position of 1-chloromethylnaphthalenes in 2-methyltetrahydrofuran under mild conditions to afford 1-(N,N-dimethylamino)-4-alkylnaphthalenes in good to high yields. The halogen atom remained intact during the dimethylamination of 1-chloromethylnaphthalenes. A P,N bidentate ligand was conveniently synthesized and successfully utilized as the ligand in the Kumada-Corriu reaction.

Inherent vs Apparent Chemoselectivity in the Kumada-Corriu Cross-Coupling Reaction.

The Kumada-Corriu reaction is a powerful tool for C-C bond formation, but is seldom utilized due to perceived chemoselectivity issues. Herein, we demonstrate that high-yielding couplings can occur in the presence of many electrophilic and heterocyclic functional groups. Our strategy is mechanically based, matching oxidative addition rates with the rate of syringe pump addition of the Grignard reagent. The mechanistic reason for the effectiveness of this strategy is uncovered by continuous-infusion ESI-MS studies.

ChemInform Abstract: Stereoretentive Pd‐Catalyzed Kumada—Corriu Couplings of Alkenyl Halides at Room Temperature.

Stereoselective palladium-catalyzed Kumada–Corriu reactions of functionalized alkenyl halides and a variety of Grignard reagents, including those bearing β-hydrogen atoms and sensitive functional groups, can be carried out at room temperature using a new combination of reagents.

Stereoretentive Pd-catalyzed Kumada-Corriu couplings of alkenyl halides at room temperature.

Stereoselective palladium-catalyzed Kumada–Corriu reactions of functionalized alkenyl halides and a variety of Grignard reagents, including those bearing β-hydrogen atoms and sensitive functional groups, can be carried out at room temperature using a new combination of reagents.

Sol–Gel Catalysts as an Efficient Tool for the Kumada-Corriu Reaction in Continuous Flow

A multichannel microreactor was fabricated to perform metal-catalyzed reactions and its efficiency was evaluated by comparing the yields and rates obtained within the micro-environment with batch processes. The microreactor was realized in glass so as to be compatible with a wide range of solvents and designed with a geometry suitable to increase the catalytic surface area and to ensure a uniform distribution of velocity and temperature. The nickel catalyst assessed was supported over the channel walls of the microreactor by gelling under controlled conditions by utilizing a silica solution containing Ni(II) salts. The sol–gel procedure allowed a porous support with a specific surface area of 387 ± 1 m2/g and catalyst particle size of 4.3 ± 1.1 nm to be generated. The multichannel microreactor was found to dramatically decrease the reaction time for the Kumada-Corriu C–C-cross coupling reactions by four orders of magnitude and to allow a three-fold increase in the yields of a biaryl compound compared with batch reactions.

ChemInform Abstract: Palladium‐Catalysed Coupling Reactions

AbstractReview: 116 refs.

Palladium-Catalyzed Cross-Coupling Reaction of Secondary Benzylic Bromides with Grignard Reagents

A mild palladium-catalyzed Kumada-Corriu reaction of secondary benzylic bromides with aryl and alkenyl Grignard reagents has been developed. In the presence of the Xantphos ligand, the undesired beta-elimination pathway is minimized, affording the corresponding cross-coupling products in acceptable to good yields. The reaction proceeds with inversion of the configuration.

Leached nickel promotes catalysis using supported Ni(II) complex precatalysts in Kumada-Corriu reactions

Ni(II) acetate is immobilized onto diamine ligands anchored to (i) a cross-linked poly(styrene) support and (ii) a mesoporous silica support. These anchored Ni(II) materials are successfully used to promote Kumada-Corriu reactions of 4-bromoanisole with phenylmagnesium chloride. Leaching studies utilizing filtration tests, analysis of recycle kinetics, elemental analysis, selective poisoning tests, and “three phase tests” indicate that an active catalytic species is associated with leached, soluble nickel. The cause of leaching is associated with the presence of the Grignard reagent. The use of anchored 3-iodopropyl groups for “three phase testing” of heterogeneity in Kumada-Corriu reactions is demonstrated. Polymer bound triphenyl phosphine is presented as a material for selective poisoning of soluble nickel in Kumada-Corriu reactions.

Synthesis, characterization and catalytic behaviors of neutral nickel complexes: Arylnickel N-alkyl-6-(1-(arylimino)ethyl)picolinamide

A series of novel neutral nickel complexes, aryl (phenyl or naphthyl) nickel N-alkyl-6-(1-(arylimino)ethyl)picolinamides, were synthesized and characterized by NMR and IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction analyses of the complexes C2, C3 and C7 reveal distorted square-planar geometry along with the molecular structure of one free ligand L1. On activation with diethylaluminum chloride (Et 2AlCl), the nickel complexes exhibited moderate catalytic activities for ethylene oligomerization, and the catalytic activity was up to 2.45 × 10 5 g mol −1(Ni) h −1 in the presence of 1 equiv. PPh 3. Moreover, these complexes also exhibit moderate activities for Kumada–Corriu reaction and polymerization of methyl methacrylate.

Anchored palladium bipyridyl complex in nanosized MCM-41: a recyclable and efficient catalyst for the Kumada–Corriu reaction

A palladium bipyridyl complex anchored onto nanosized mesoporous silica MCM-41 catalyzed the cross-coupling of aryl iodides or bromides with Grignard reagents to provide the corresponding biaryls in high yields. The reaction proceeded smoothly with an equal molar amount of substrate and Grignard reagent in the presence of 0.2–0.02 mol % of catalyst in THF at 50 °C or under refluxing conditions. The catalyst prepared may be used in a very low percentage, recovered after reaction, and re-used.

Pyridin- and quinolinylidene nickel carbene complexes as effective catalysts for the Grignard cross-coupling reaction

A series of complex compounds that contain N-heterocyclic carbene (NHC) and N-heterocyclic carbene ligands with a remote heteroatom ( rNHC) have been prepared in good yields and characterized. [Cl(NHC)(PPh 3) 2Ni]BF 4 and [Cl( rNHC)(PPh 3) 2Ni]BF 4 also combine the stability of carbene complexes with the activity of phosphine complexes and some are active and effective precatalysts for aryl-coupling in the Kumada–Corriu reaction. Aryl chlorides can be used as substrates. Their performance in catalysis as well as their easy preparation make the new compounds superior to other comparable mixed carbene–phosphine compounds known thus far.

Synthesis of Marine Polyacetylenes Callyberynes A—C by Transition‐Metal‐Catalyzed Cross‐Coupling Reactions to sp Centers.

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Synthesis of Marine Polyacetylenes Callyberynes A−C by Transition-Metal-Catalyzed Cross-Coupling Reactions to sp Centers

Efficient total syntheses of the sponge-derived hydrocarbon polyacetylenes callyberynes A-C have been achieved using metal-catalyzed cross-coupling reactions of highly unsaturated 1,3-diyne fragments as the key steps, namely: Cadiot-Chodkiewicz reaction under Alami's optimized conditions (sp-sp), sequential Sonogashira reaction of a cis,cis-divinyl dihalide (sp2-sp), and Kumada-Corriu reaction of an unactivated alkyl iodide (sp3-sp). This last approach constitutes the first application of a metal-catalyzed sp3-sp Kumada-Corriu cross-coupling reaction to the synthesis of a natural product.

Kumada—Corriu Reactions of Alkyl Halides with Alkynyl Nucleophiles.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Grignard cross-coupling catalyzed by chiral phosphino–quincorine and phosphino–quincoridine derivatives

New β-aminoalkylphosphines with a stereogenic nitrogen center have been synthesized from quincorine and quincoridine. Nickel catalysts were studied for their enantioselectivity in the asymmetric Kumada–Corriu reaction. The (2 S,4 S,5 R)-2-diphenylphosphinomethyl-5-ethyl-quinuclidine–nickel complex led to e.e. of 85% for the cross-coupling of 1-phenylethylmagnesium chloride with vinyl bromide.

Kumada-Corriu reactions in a pressure-driven microflow reactor.

Reaction rates for the Kumada reaction (of Grignard reagents with aryl halides) catalysed by an immobilised nickel(II) catalyst have been shown to be enhanced when the reaction is carried out in a pressure driven microreactor (internal diameter 100-200 microm) rather than with conventional batch reaction techniques.