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Sustainable metal catalysis in C?H activation

The omnipresence of C?H bonds in organic compounds renders them highly attractive targets for the installation of functional groups towards the construction of valuable molecular scaffolds. Consequently, C?H activation has extended beyond scientific curiosity and has evolved from being a concept of fundamental interest to constituting an important, modern tool of organic synthesis. The intensity of research efforts and accompanying discussion surrounding this topic has given rise to a plethora of innovative, cutting-edge advancements. These advancements demonstrate the vast potential of the C?H activation approach regarding the design of highly efficient and selective catalytic methodologies for the synthesis of fine chemicals, natural products, and advanced materials. However, the overall sustainable nature of this approach, emanating from some of its main attributes such as atom- and step-economy, is compromised by the frequent need of homogeneous catalysts based on rare, expensive, and even toxic noble transition metals. In order to address this issue and achieve truly sustainable catalytic C?H activation, significant research efforts have focused on the development of homogeneous catalytic systems based on more abundant, first row transition metals. In this respect, various catalytic protocols involving the use of highly abundant, inexpensive, readily available, and also biorelevant metals such as Mg, Ca, Mn, Fe, Cu, and Zn have been elegantly developed in recent years. Catalysts based on the aforementioned sustainable metals exhibit unique behavior in terms of reactivity/selectivity and their use does not only provide an alternative to noble metal catalysis, but also expands the scope of C?H activation. The present review provides a comprehensive examination of selected works that highlight the evolution and growing importance of this merge of two vibrant concepts in modern organic synthesis: sustainable metal catalysis and C?H activation.

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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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1- [2- (2, 4-DIMETHYLPHENYLSULFANYL) -PHENYL] PIPERAZINE AS A COMPOUND WITH COMBINED SEROTONIN REUPTAKE, 5-HT3 AND 5-HT1A ACTIVITY FOR THE TREATMENT OF COGNITIVE IMPAIRMENT

1-[2-(2,4-dimethylphenylsulphanyl)phenyl]piperazine exhibits potent activity on SERT, 5-HT3 and 5-HT1A and may as such be useful for the treatment of cognitive impairment, especially in depressed patients.

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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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Imidazo-phenanthroline ligands as a convenient modular platform for the preparation of heteroleptic Cu(I) photosensitizers

The capture and storage of solar energy is a promising option to overcome current energy issues. To put such systems into practice, molecular photosensitizers should be based on abundant metals and possess a strong absorption capability for visible light. Therefore, a systematic series of four novel heteroleptic Cu(I) complexes of the type [(PP)Cu(NN)]+ (with PP = xantphos and NN = different diimine ligands) has been prepared. As an essential feature, these copper photosensitizers contain an imidazole moiety at the backbone of the diimine ligand, which increases the aromatic pi-system compared to phenanthroline type ligands. Moreover, 2-(4-bromophenyl)-1-phenyl-1H-imidazo-[4,5-f ][1,10]phenanthroline was used as a starting point and modular platform for gradually extended diimine ligands. Suzuki cross-coupling was applied to introduce different kind of substituents in the back of this ligand. Afterwards, a combination of NMR spectroscopy, mass spectrometry, X-ray analysis, cyclic voltammetry, UV/vis and emission spectroscopy was used to investigate the structural, electrochemical and photophysical properties of these compounds. As a result, a reversible reduction, strongly increased extinction coefficients and significantly redshifted absorption maxima ( > 20 nm) were found compared to traditional Cu(I) photosensitizers without an imidazo moiety. Moreover, these compounds show a bright emission in the solid state.

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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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Gold as a catalyst. Part I. Nucleophilic addition to the triple bond

This paper is the first in a series of reviews of the state of-the-art in gold catalysis in organic synthesis and covers the literature over the past decade. The first review addresses the problem of the nucleophilic addition to the triple bond. Gold catalysts used in the hydroamination of alkynes and the addition of oxygen-containing nucleophiles and thiols are considered. The data concerning intra- and intermolecular types of transformations are given separately. The alpha, alpha-nucleophilic addition and Au carbene intermediates are 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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SULFOXIMINE SUBSTITUTED QUINAZOLINES FOR PHARMACEUTICAL COMPOSITIONS

This invention relates to novel sulfoximine substituted quinazoline derivatives of formula I wherein Ar, R1 and R2 are as defined herein, and their use as MNK1 (MNK1a or MNK1b) and/or MNK2 (MNK2a or MNK2b) kinase inhibitors, pharmaceutical compositions containing the same, and methods of using the same as agents for treatment or amelioration of MNK1 (MNK1a or MNK1b) and/or MNK2 (MNK2a or MNK2b) mediated disorders.

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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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Complexes with protic (NH,NH and NH,NR) N-heterocyclic carbene ligands

The review describes methods for the preparation of complexes bearing protic NHC ligands, i.e. NHCs featuring an NH,NH or NH,NR substitution pattern. The protic NHC ligands are easily functionalized at the ring nitrogen atoms after N-H deprotonation. Thus the introduction of various functional groups at the ring nitrogen atoms is possible giving access to new complexes with NHC ligands and even allowing the linkage of individual protic NHCs to give macrocyclic ligands with NHC donors. Selected applications for complexes bearing protic NHCs will be described.

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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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Highly Efficient Palladium-Catalyzed Allylic Alkylation of Cyanoacetamides with Controllable and Chemoselective Mono- and Double Substitutions

The front cover artwork for Issue 22/2016 is provided by Zi-Wei Gao and Li-Wen Xu’s group of Shaanxi Normal University. The image shows a novel palladium catalyst system combined with a triazine-modified new phosphine ligand that was developed successfully for the catalytic allylic alkylation of various cyanoacetamides. See the Full Paper itself at http://dx.doi.org/10.1002/cctc.201601021.

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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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Generating Active L-Pd(0) via Neutral or Cationic pi-Allylpalladium Complexes Featuring Biaryl/Bipyrazolylphosphines: Synthetic, Mechanistic, and Structure-Activity Studies in Challenging Cross-Coupling Reactions

Two new classes of highly active yet air- and moisture-stable pi-R-allylpalladium complexes containing bulky biaryl- and bipyrazolylphosphines with extremely broad ligand scope have been developed. Neutral pi-allylpalladium complexes incorporated a range of biaryl/bipyrazolylphosphine ligands, while extremely bulky ligands were accommodated by a cationic scaffold. These complexes are easily activated under mild conditions and are efficient for a wide array of challenging C-C and C-X (X = heteroatom) cross-coupling reactions. Their high activity is correlated to their facile activation to a 12-electron-based L-Pd(0) catalyst under commonly employed conditions for cross-coupling reactions, noninhibitory byproduct release upon activation, and suppression of the off-cycle pathway to form dinuclear (mu-allyl)(mu-Cl)Pd2(L)2 species, supported by structural (single crystal X-ray) and kinetic studies. A broad scope of C-C and C-X coupling reactions with low catalyst loadings and short reaction times highlight the versatility and practicality of these catalysts in organic synthesis.

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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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Multinuclear Copper Hydride Complexes Supported by Polyphosphine Ligands

Copper hydride compounds have attracted interest in diverse fields as base metallic material in place of rare and noble metals, which have widely been utilized in hydrogenation catalysts, hydrogen storage, and electrochemical materials. Since the first report on the synthesis of copper hydride complex [Cu6H6(PPh3)6] in 1971, copper hydride reagents have been utilized in a variety of organic transformation. While well-characterized copper hydride complexes have been long limited to a few examples, recently several research groups have reported the synthesis of phosphine-stabilized copper hydride complexes with various metal-frameworks and unique reactivity. Here we review recent progress on the synthesis and structures of copper hydride complexes supported by phosphine ligands, including di-, tri-, and tetraphosphines, and also describe their reactivity with CO2.

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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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Oxometalate and phosphine ligand co-protected silver nanoclusters: Ag28(dppb)6(MO4)4 and Ag32(dppb)12(MO4)4(NO3)4

Thiols, alkynyls and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters, while oxometalates as inorganic ligands have almost been neglected in this field. Here, we used oxometalates (e.g., MoO42- and WO42-) as protecting ligands along with phosphines, such as 1,4-bis(diphenylphosphino)butane (dppb), to design and synthesize a new class of silver nanoclusters including Ag28(dppb)6(MoO4)4, Ag28(dppb)6(WO4)4 and Ag32(dppb)12(MoO4)4(NO3)4. Each cluster consists of a two-shell Ag4@Ag24 core protected by 4 oxometalates. These clusters exhibit similar optical absorption and photoluminescence properties that are not dependent on surface ligands. Furthermore, the electronic structure analysis shows that the clusters are 20-electron “superatoms”. This work demonstrates that oxometalates can play a key role in the formation of silver nanoclusters, and the effect of oxometalates should be considered in the design and synthesis of metal nanoclusters.

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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