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A simple and efficient copper-catalyzed procedure for the hydrosilylation of hindered and functionalized ketones

The catalytic hydrosilylation of highly hindered and functionalized ketones is described. The combination of inexpensive catalyst precursors, CuCl and NHC¡¤HX (NHC = N-heterocyclic carbene), leads to a highly efficient reduction mediator for the preparation of silyl ethers from unfunctionalized and functionalized alkyl, cyclic, bicyclic, aromatic, and heteroaromatic ketones. A series of catalyst precursors have been structurally characterized and a catalyst-structure activity relationship is discussed.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis and structural characterization of a gold(I) complex containing 1,3-dimethylcyanurate ligand

The gold(I) complex [Au(DMC)(PPh3)] (1) (DMC?=?1,3-dimethylcyanurate) was synthesized and characterized by elemental analysis, FT-IR, 1H, 13C, 31P NMR and FAB mass spectroscopies. The structure of the complex was determined by X-ray diffraction and crystallizes in the triclinic space group P?1 with Z?=?2. The gold(I) ion in complex 1 is coordinated by DMC ligand and PPh3 ligand, resulting in a slightly distorted linear structure. Molecules of 1 are connected via intermolecular C?H¡¤¡¤¡¤O hydrogen bonds, which lead to the formation of supramolecular network. Other intramolecular interactions which include Au¡¤¡¤¡¤O contacts [Au¡¤¡¤¡¤O25 3.045(1) and Au¡¤¡¤¡¤O29 3.164(1)?] were observed.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Cobalt Complexes as an Emerging Class of Catalysts for Homogeneous Hydrogenations

ConspectusCatalytic hydrogenation using molecular hydrogen represents a green and practical approach for reductions of all kinds of organic chemicals. Traditionally, in the majority of these processes the presence of transition metal catalysts is required. In this regard, noble-metal-based catalysts have largely been implemented, such as the application of iridium, palladium, rhodium, ruthenium, and others. Recently, the employment of earth-abundant 3d metals has emerged to replace the utilization of scarce noble metals because of their availability, lower cost, and often reduced toxicity. In this respect, several cobalt complexes, in the form of either molecularly well-defined or in situ-formed complexes, are receiving increasing attention from the scientific community. Importantly, the stability and reactivity of the complexes have greatly been supported by multidentate ligands under steric and/or electronic influences. For instance, tridentate or tetradentate phosphine ligands indirectly tune the reactivity of the metal center to accelerate the overall process, whereas direct participation of the ligand in pincer-type complexes through ligand-metal cooperation regulates the elementary steps in the catalytic cycle.In this Account, we emphasize specifically the advancements in cobalt-catalyzed hydrogenations using molecular hydrogen accomplished in our group. A variety of substrate classes ranging from simple molecules (e.g., carbon dioxide) to complex compounds were explored under the mild and efficient catalytic conditions. Notable examples include the reduction of carbon dioxide to afford either formates using a Co(BF4)2¡¤6H2O/Tetraphos catalyst system or methanol employing a Co(acac)3/Triphos complex in the presence of HNTf2. As interesting examples of the synthesis of fine chemicals, cobalt-promoted hydrogenations of nitriles to primary amines and reductive alkylations of indoles using carboxylic acids as alkylating agents are highlighted. Moreover, highly selective hydrogenations of N-heteroarenes under additive-free conditions were possible by the application of specific cobalt complexes. More recently, a set of carboxylic esters could be hydrogenated to the corresponding alcohols with high efficiency by the use of a well-defined cobalt-PNP pincer catalyst. In particular, the decent reactivity of cobalt catalysts enabled high selectivity and functional group tolerance to be achieved. Throughout our studies, it was found that the pairing of a suitable cobalt precursor and an appropriate tridentate or tetradentate phosphine ligand plays a crucial role harnessing the desired reactivity, while other monodentate and bidentate phosphine ligands showed no reactivity in these investigations. Our developments could provide supervisory information for the future exploration of cobalt-catalyzed hydrogenation reactions and other types of reactions involving cobalt catalysis. Furthermore, relevant contributions from other groups, remaining challenges, and future perspectives in this research area are also presented.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Process for the preparation of aminodiphenylamines

Die Erfindung betrifft ein Verfahren zur Herstellung von Aminodiphenylaminen, insbesondere von 4-Aminodiphenylamin (4-ADPA), durch Umsetzung von Nitrohalogenbenzolen mit Anilinen in Gegenwart einer Base sowie eines Kupfer-Phosphor-Komplexes und anschliessender Hydrierung der intermediaer gebildeten Nitrodiphenylaminen.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Design and Optimization of Catalysts Based on Mechanistic Insights Derived from Quantum Chemical Reaction Modeling

Until recently, computational tools were mainly used to explain chemical reactions after experimental results were obtained. With the rapid development of software and hardware technologies to make computational modeling tools more reliable, they can now provide valuable insights and even become predictive. In this review, we highlighted several studies involving computational predictions of unexpected reactivities or providing mechanistic insights for organic and organometallic reactions that led to improved experimental results. Key to these successful applications is an integration between theory and experiment that allows for incorporation of empirical knowledge with precise computed values. Computer modeling of chemical reactions is already a standard tool that is being embraced by an ever increasing group of researchers, and it is clear that its utility in predictive reaction design will increase further in the near future.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Attapulgite-anchored Pd complex catalyst: a highly active and reusable catalyst for C?C coupling reactions

Natural clay, attapulgite was successfully employed to prepare reusable heterogeneous catalyst of ATP?APTES?Pd through simple and green steps. The catalyst was characterized by ICP, IR, XRD, XPS, SEM, and TG. The novel complex exhibited excellent activity for a wide scope of Suzuki and Heck cross-coupling reactions without phosphine ligand, respectively. Remarkably, the catalyst is easy to separate, stable and can be reused several times in good activity without any additional activation treatment.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Computational Studies of Carboxylate-Assisted C-H Activation and Functionalization at Group 8-10 Transition Metal Centers

Computational studies on carboxylate-assisted C-H activation and functionalization at group 8-10 transition metal centers are reviewed. This Review is organized by metal and will cover work published from late 2009 until mid-2016. A brief overview of computational work prior to 2010 is also provided, and this outlines the understanding of carboxylate-assisted C-H activation in terms of the “ambiphilic metal-ligand assistance” (AMLA) and “concerted metalation deprotonation” (CMD) concepts. Computational studies are then surveyed in terms of the nature of the C-H bond being activated (C(sp2)-H or C(sp3)-H), the nature of the process involved (intramolecular with a directing group or intermolecular), and the context (stoichiometric C-H activation or within a variety of catalytic processes). This Review aims to emphasize the connection between computation and experiment and to highlight the contribution of computational chemistry to our understanding of catalytic C-H functionalization based on carboxylate-assisted C-H activation. Some opportunities where the interplay between computation and experiment may contribute further to the areas of catalytic C-H functionalization and applied computational chemistry are identified.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Efficient general procedure to access a diversity of gold(0) particles and gold(I) phosphine complexes from a simple HAuCl4 source. Localization of homogeneous/heterogeneous system’s interface and field-emission scanning electron microscopy study

Soluble gold precatalysts, aimed for homogeneous catalysis, under certain conditions may form nanoparticles, which dramatically change the mechanism and initiate different chemistry. The present study addresses the question of designing gold catalysts, taking into account possible interconversions and contamination at the homogeneous/heterogeneous system’s interface. It was revealed that accurate localization of boundary experimental conditions for formation of molecular gold complexes in solution versus nucleation and growth of gold particles opens new opportunities for well-known gold chemistry. Within the developed concept, a series of practical procedures was created for efficient synthesis of soluble gold complexes with various phosphine ligands (R3P)AuCl (90-99% yield) and for preparation of different types of gold materials. The effect of the ligand on the particles growth in solution has been observed and characterized with high-resolution field-emission scanning electron microscopy (FE-SEM) study. Two unique types of nanostructured gold materials were prepared: hierarchical agglomerates and gold mirror composed of ultrafine smoothly shaped particles.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Theoretical insights on the C-C bond reductive elimination from Co(III) center

The density-functional theory (DFT) calculations using B3LYP functional were performed to inspect the mechanism of the reductive elimination of ethane from a cobalt (III) dimethyl complex, (PMe3)3Co(CH3)2I. Three different pathways, i.e., radical mechanism (path A), concerted C-C bond formation (path B) and alpha-hydride elimination (path C) were studied for the reductive elimination reaction. A PMe3 ligand of the hexa-coordinated cobalt complex dissociates to form penta-coordinated complex. The penta-coordinated complex undergoes reductive elimination reaction. The calculated Gibbs free energy for the formation of methyl radical is 27.6 kcal/mol. Path B involving concerted C-C bond formation shows the activation energy barrier of 12.8 kcal/mol for the reductive elimination reaction. The calculated activation energy barrier for alpha-hydride elimination mechanism is 53.1 kcal/mol. Path B shows the lowest activation energy barrier of 12.8 kcal/mol, however, this value is much lower than the experimentally determined activation energy (25.0 kcal/mol). With MN12SX functional, the activation energy value improves to 20.8 kcal/mol which is close to the experimental value.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Investigation of green and sustainable solvents for direct arylation polymerization (DArP)

Direct arylation polymerization (DArP) is an emerging method for conjugated polymer synthesis. It alleviates typical synthetic routes from toxic, hazardous materials, such as pyrophorphoric organolithium or highly-toxic stannane reagents. The progress and development of synthetic methodologies for DArP have allowed for the preparation of conjugated polymers with a minimization or exclusion of undesired couplings, such as branching (beta) defects and donor-donor or acceptor-acceptor homocouplings. This has allowed for conjugated polymers prepared using DArP to converge upon or surpass the performance of polymers prepared using conventional polymerization methods, e.g. Stille or Suzuki, when integrated into polymer bulk-heterojunction solar cells. Considering that DArP has the potential to become the industrial-scale method for conjugated polymer synthesis, determining the compatability of environmentally benign, non-hazardous, and low-cost solvents with DArP is imperative. Herein, we report the application of green and sustainable solvents, such as 2-methyltetrahydrofuran, cyclopentyl methyl ether, diethylcarbonate, and gamma-valerolactone, for DArP towards the preparation of poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole) (PPDTBT) and poly(3-hexylthiophene) (P3HT), where optimal conditions are derived based on the molecular weight, yield, and characterization (NMR, XRD, and UV-vis) for the aforementioned polymers. We find that cyclopentyl methyl ether (CPME) provides the best polymerization products with an Mn up to 41 kDa for PPDTBT and with yields up to 98%, which is the highest reported to our knowledge for this polymer prepared using DArP. Application of CPME to P3HT resulted in Mn values of 12 kDa with 93% regio-regularity (RR) and no detectable beta-defects.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate