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BN/CC isosterism has emerged as a viable strategy to expand the chemical space of organic molecules. In particular, the application of BN/CC isosterism to arenes has received significant attention due to the vast available chemical space provided by aromatic hydrocarbons. The synthetic efforts directed at assembling novel aromatic BN heterocycles have resulted in the discovery of new properties and functions in a variety of fields including biomedical research, medicinal chemistry, materials science, catalysis, and organic synthesis. This tutorial review specifically covers recent advances in synthetic technologies that functionalize assembled boron-nitrogen (BN) heterocycles and highlights their distinct reactivity and selectivity in comparison to their carbonaceous counterparts. It is intended to serve as a state-of-the-art compendium for readers who are interested in the reaction chemistry of BN heterocycles.

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Reference:
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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Ligands are essential for controlling the reactivity and selectivity of reactions catalysed by transition metals. Access to large phosphine ligand libraries has become an essential tool for the application of metal-catalysed reactions industrially, but these existing libraries are not well suited to new catalytic methods based on non-precious metals (for example, Ni, Cu and Fe). The development of the requisite nitrogen-and oxygen-based ligand libraries lags far behind that of the phosphines and the development of new libraries is anticipated to be time consuming. Here we show that this process can be dramatically accelerated by mining for new ligands in a typical pharmaceutical compound library that is rich in heterocycles. Using this approach, we were able to screen a structurally diverse set of compounds with minimal synthetic effort and identify several new ligand classes for nickel-catalysed cross-electrophile coupling. These new ligands gave improved yields for challenging cross-couplings of pharmaceutically relevant substrates compared with those of those of previously published ligands.

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Reference:
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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This review presents a systematic survey of the literature (through the end of 2017) that reports on the reactivity of 3-pyrrolin-2-ones. The discussion starts with site-specific reactivity (N, C2, C3, C4, and C5), followed by reactions across the C3?C4 pi-bond, and then transformations of 3-pyrrolin-2-ones to other heterocycles. Throughout the narrative, there is an attempt to show pertinent examples of 3-pyrrolin-2-ones being used as building blocks and intermediates leading to natural products and other complex heterocyclic targets. The review article contains a total of 601 references.

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Reference:
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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This review focuses on the evolution of the use of osmium complexes as catalysts in the hydrogenation and isomerization of olefins. Osmium systems show good catalytic activities and selectivities in the hydrogenation of olefins via both dihydrogen and transfer hydrogenation. Such systems therefore have significant potential to become a powerful tool in organic synthesis.

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Reference:
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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New chiral ferrocenyldiphosphine ligands (R)-(S)-3 and (R)-(S)-4 were prepared. The ligands were employed in Ru(II) catalyzed asymmetric transfer hydrogenation of ketones to give corresponding secondary alcohols. Up to 99% conversion with 90% e.e. was obtained on Ru(DMSO)4Cl2/4 in transfer hydrogenation of acetophenones with propan-2-ol.

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Reference:
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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We describe here the synthesis and structural characterization of two new classes of ambiphilic, N-boryl imine ligands, wherein boron is associated with a Lewis basic imine nitrogen. These ligands can be easily generated in two steps from the corresponding pyridinyl- and phosphinyl-tethered aldehydes. 11B NMR analysis suggests the association of the Lewis acidic boron to either the pyridine unit or via intermolecular acid/base interactions with the imine. Both of these ligands can coordinate to palladium, and their structures were confirmed by X-ray crystallography..

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Reference:
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

Archives for Chemistry Experiments of Benzyldiphenylphosphine

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Our results show that the stereoselectivity of the Wittig-reaction can be controlled by the variation of substituents in accord with the ORDERING CONCEPT OF ALTERNATIV PRINCIPLES (individual pairs, known and unknown classes of alternatives).The “all-phenyl Wittig-system” having three phenyl groups on phosphorous two in ylid- and aldehyd-position was chosen as a standard for our investigations.Differentiation in ylid-position and compensation on phosphorous and aldehyd-position were observed by the comparison of “patterns”.Consequently, most of the selectivity rules of Wittig-reactions can be explained by the differentiation through alternatives in the ylid-position.Inversion or conservation of the “patterns” of measured data points to the variation in structure of starting materials, reaction rates and selectivities.Amount-controls were also described in certain systems.

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Reference:
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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Some new organometallics of ruthenium(II) of the type [RuCl2(COD)(CO)L] (1a-f) and [RuCl2(COD)L2] (2a-f) (where L is substituted tertiary phosphines), have been synthesized by using precursors [RuCl2(COD)(CO)(CH3CN)] (1) and [RuCl2(COD)(CH3CN)2] (2) with the substituted tertiary phosphine ligands in 1:1 and 1:2 molar ratio. The organometallics (2a-f) have been further reacted with carbonmonoxide to produce compounds of the type [RuCl2(CO)L2] (3a-f). These compounds were characterized by elemental analysis, IR, NMR (1H, 13C and 31P), mass and electronic spectral data. The catalytic activity of all these organometallics were studied and found that they are efficient catalysts for hydrolysis of etofibrate. The hydrolyzed product was separated by column chromatography and the percent yields are found in the range of 98.6-99.1%.

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Reference:
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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The transfers of oxygen from nitrogen to phosphorus in the conversions of 1 to 2 and 3 to 4 are shown by kinetic, solvent-labeling, and double-labeling criteria to be intramolecular reactions. This information in conjunction with the stabilities of 13 and 14 is taken to rule out the mechanisms of classic linear SN2 substitutions at oxygen or nitrogen, biphilic insertion, or a radical chain reaction and to favor reactions via a 10-P-5 species (18). These results appear to provide the first experimental demonstration that oxygen can be transferred at an oblique angle.

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Reference:
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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A polyaromatic tube with a subnanometer-sized cavity was efficiently prepared on a gram-scale through the stereo-controlled cyclotrimerization of a diphenylanthracene derivative as a key step. The facile exterior alkylation of the polyaromatic framework leads to a moderately fluorescent tube (R=-OC10H21; PhiF=20 %) in the solid state. The emission intensity of the solid-state alkyl-substituted tube is remarkably enhanced upon heating (up to 1.6 times, PhiF=31 %) as well as doping with fluorescent dyes (up to 4.2 times, PhiF=83 %) through efficient energy transfer.

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Reference:
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