Transformation of carbon-oxygen into carbon-carbon bonds mediated by low-valent nickel species
TL;DR: Etude de la substitution de groupes alcoxy d'enols ethers (methoxy-1 cyclohexenes, methoxy- 1 alcenes-1, benzofuranne, dihydro-2,3 furanne) par l'intermediaire de la reaction de Grignard catalysee par le dichlorure de bis-triphenylphosphine-nickel
Abstract: Etude de la substitution de groupes alcoxy d'enols ethers (methoxy-1 cyclohexenes, methoxy-1 alcenes-1, benzofuranne, dihydro-2,3 furanne) et de (methyl aryl) ethers par l'intermediaire de la reaction de Grignard catalysee par le dichlorure de bis-triphenylphosphine-nickel
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TL;DR: Nickel-Catalyzed Cross-Couplings Involving Carbon-Oxygen Bonds Brad M. Rosen, Kyle W. Quasdorf, Daniella A. Wilson, Na Zhang, Ana-Maria Resmerita, Neil K. Garg, and Virgil Percec report on cross-coupling strategies for high-performance liquid chromatography of carbon dioxide and nitrogen.
Abstract: Nickel-Catalyzed Cross-Couplings Involving Carbon-Oxygen Bonds Brad M. Rosen, Kyle W. Quasdorf, Daniella A. Wilson, Na Zhang, Ana-Maria Resmerita, Neil K. Garg,* and Virgil Percec* Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States
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TL;DR: A broad range of aryl electrophiles, which are conventionally challenging, by applying palladium catalysts can now be coupled efficiently with boron reagents in the presence of nickel catalysts.
Abstract: In the transition-metal-catalyzed cross-coupling reactions, the use of the first row transition metals as catalysts is much more appealing than the precious metals owing to the apparent advantages such as cheapness and earth abundance. Within the last two decades, particularly the last five years, explosive interests have been focused on the nickel-catalyzed Suzuki–Miyaura reactions. This has greatly advanced the chemistry of transition-metal-catalyzed cross-coupling reactions. Most notably, a broad range of aryl electrophiles such as phenols, aryl ethers, esters, carbonates, carbamates, sulfamates, phosphates, phosphoramides, phosphonium salts, and fluorides, as well as various alkyl electrophiles, which are conventionally challenging, by applying palladium catalysts can now be coupled efficiently with boron reagents in the presence of nickel catalysts. In this review, we would like to summarize the progress in this reaction.
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TL;DR: Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons.
Abstract: Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from competing hydrogenolysis of aliphatic C-O bonds and hydrogenation of the arene. Here, we report hydrogenolyses of aromatic C-O bonds in alkyl aryl and diaryl ethers that form exclusively arenes and alcohols. This process is catalyzed by a soluble nickel carbene complex under just 1 bar of hydrogen at temperatures of 80 to 120°C; the relative reactivity of ether substrates scale as Ar-OAr>>Ar-OMe>ArCH2-OMe (Ar, Aryl; Me, Methyl). Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons.
684 citations
TL;DR: Recent efforts toward Fe, Co, and Ni catalyzed "inert" chemical bond activation are summarized, indicating that the catalytic efficacy in cross coupling between aryl bromides and arenes under mild conditions was not the privilege of several noble metals.
Abstract: ConspectusActivation of inert chemical bonds, such as C–H, C–O, C–C, and so on, is a very important area, to which has been drawn much attention by chemists for a long time and which is viewed as one of the most ideal ways to produce valuable chemicals. Under modern chemical bond activation logic, many conventionally viewed “inert” chemical bonds that were intact under traditional conditions can be reconsidered as novel functionalities, which not only avoids the tedious synthetic procedures for prefunctionalizations and the emission of undesirable wastes but also inspires chemists to create novel synthetic strategies in completely different manners.Although activation of “inert” chemical bonds using stoichiometric amounts of transition metals has been reported in the past, much more attractive and challenging catalytic transformations began to blossom decades ago. Compared with the broad application of late and noble transition metals in this field, the earth-abundant first-row transition-metals, such as ...
551 citations