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Chiral pyridine-containing ligands in asymmetric catalysis

In this article, an overview of the investigations on chiral py-containing ligands in asymmetric catalysis that have carrried out in the past years is provided. The ligands are divided into different types based on the number of pyridine moieties present and the way they are connected in the ligands, namely monopyridine, dipyridine (two pyridines connected by a bridge), bipyridine, phen(1,10-phenanthroline), terpyridine and oligopyridine. In each section, the synthetic strategies for each type of ligands are discussed and representative examples are given. Selected important results in asymmetric catalysis are mentioned.

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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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Novel allyl cobalt phosphine complexes: Synthesis, characterization and behavior in the polymerization of allene and 1,3-dienes

Novel allyl cobalt complexes, i.e., (eta3-C4H7)(eta4-C4H6)Co(PCyPh2) (1), (eta3-C4H7)(eta4-C4H6)Co(PMePh2) (2) and (eta3-C5H9)(eta4-C5H8)Co(PMePh2) (3), were synthesized by reacting CoCl2(PRPh2)2 (R = methyl, cyclohexyl) with 1,3-butadiene or isoprene in presence of metallic zinc. The complexes were fully characterized by Nuclear Magnetic Resonance (NMR) spectroscopy (1H and 2D experiments); in case of 1, single crystals, suitable for X-ray analysis, were obtained and the molecular structure was determined. The allyl cobalt phosphine complexes alone gave highly crystalline 1,2 polymers from 1,2-propadiene, but they did not polymerize 1,3-dienes. Nevertheless, in the presence of a stoichiometric amount of methylaluminoxane (MAO), they were able to polymerize 1,3-butadiene and substituted 1,3-butadienes such as isoprene, (E)-1,3-pentadiene, (E)-1,3-hexadiene, and (E)-3-methyl-1,3-pentadiene. Specifically, 1/MAO gave predominantly syndiotactic 1,2 polymers from 1,3-butadiene and terminally substituted 1,3-butadienes (e.g., 1,3-pentadiene and 1,3-hexadiene), but it was practically not active in the polymerization of internally substituted 1,3-butadienes (e.g., isoprene and 3-methyl-1,3-pentadiene); 2/MAO and 3/MAO exhibited instead an opposite behavior, giving predominantly isotactic 1,2 polymers from 3-methyl-1,3-pentadiene, and showing very low activity in the polymerization of 1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene. The results obtained are interesting from the mechanistic point of view, and some hypotheses to explain this particular behavior were formulated.

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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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CHAPTER 8: Noncovalent interactions in hydrogenation and hydroformylation

This chapter summarizes the fundamentals of hydrogenation and hydroformylation reactions. An overview of state-of-the-art developments is presented to set the context. Subsequently, the significance of noncovalent interactions in these reactions is discussed in detail. Hydrogen bonding has been one of the leading noncovalent interactions that has been very frequently used in catalysis, including hydrogenation and hydroformylation reactions. Recent examples from the literature are presented to illustrate the role of hydrogen bonding in hydrogenation and hydroformylation. The impact of hydrogen bonding on catalyst development through self-assembly and the role of hydrogen bonding in directing a substrate to achieve high enantiomeric excess 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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Enhanced hydrogen generation from formic acid by a biomimetic ruthenium complex with a covalently bonded phosphine ligand

A series of [Ru2(CO)5(mu-SCH2CH2CH2S)PXS] complexes (Ru2-S2-PXS, X?=?phosphine ligands, S?=?1?8) have been synthesized and evaluated for their photocatalytic H2 generation efficiencies from formic acid decomposition. The [Ru2(CO)5(mu-SCH2CH2CH2S)P(o-C6H4CH3)3] (Ru2-S2-PX4) catalyst?+?P(CH3)3 ligand exhibited a high turnover frequency of 15,840?h?1 and turnover number of 24,536. A mechanistic investigation of the Ru2-S2-PX4?+?FA/TEA catalyzed photocatalytic H2 generation reaction using ATR-IR, EI-MS, and NMR techniques suggested that when Ru2-S2-PX4 was photoirradiated, the P(o-C6H4CH3)3 was dissociated from the complex to form a new species, [Ru2(CO)5(mu-SCH2CH2CH2S)]* (I). The free P(o-C6H4CH3)3 then attacks a second molecule of Ru2-S2-PX4 to form Ru2-S2-(PX4)2 and release of free CO, which is then combined with species I to form Ru2-S2. Subsequent attachment of formate ion to species Ru2-S2-PX4, Ru2-S2, and Ru2-S2-(PX4)2 to form [Ru2(CO)5(mu-SCH2CH2CH2S)]-HCOO? (II), Ru2-S2-HCOO? (II?) and Ru2-S2-PX4-HCOO? (II?), respectively. Rearrangement of complex II (or II? or II?) and evolution of CO2 generate a transient complex [Ru2(CO)5(mu-SCH2CH2CH2S)H] (III), which then undergoes a protonation process to yield complex [Ru2(CO)5(mu-SCH2CH2CH2S)H2] (IV). Release of H2 and re-incorporation of the formate anion as well as evolution of CO2 regenerates the active complex III and the cycle begins again.

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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 Pincer Complexes in Catalytic C-H Borylation: The Pincer Ligand Flips Rather Than Dearomatizes

The mechanism for the borylation of an aromatic substrate by a cobalt pincer complex was investigated by density functional theory calculations. Experimental observations identified trans-(iPrPNP)CoH2(BPin) as the resting state in the borylation of five-membered heteroarenes and 4-BPin-(iPrPNP)Co(N2)BPin as the resting state in the catalytic borylation of arene substrates. The active species, 4-R-(iPrPNP)CoBPin (R = H, BPin), were generated by reductive elimination of H2 in the former, through Berry pseudorotation to the cis isomer and N2 loss in the latter. The catalytic mechanism of the resulting Co(I) complex was computed to involve three main steps: C-H oxidative addition of the aromatic substrate (C6H6), reductive elimination of PhBPin, and regeneration of the active complex. The oxidative addition product formed through the most favorable pathway, where the breaking C-H bond of C6H6 is parallel to a line between the two phosphine atoms, leaves the complex with a distorted PNP ligand, which rearranges to a more stable complex via dissociation and reassociation of HBPin. Alternative pathways, sigma-bond metathesis, and the oxidative addition in which the breaking C-H bond is parallel to the Co-B bond are predicted to be unlikely for this Co(I) complex. The thermodynamically favorable formation of the product PhBPin via reductive elimination drives the reaction forward. The active species regenerates through the oxidative addition of B2Pin2 and reductive elimination of HBPin. In the overall reaction, the flipping (refolding) of the five-membered phosphine rings, which connects the species with two phosphine rings folded in the same direction and that with them folded in different directions, is found to play an important role in the catalytic process, as it relieves steric crowding within the PNP ligand and opens Co coordination space. Metal-ligand cooperation based on the ligand’s aromatization/dearomatization, a common mechanism for heavy-metal pincer complexes, and the dissociation of one phosphine ligand do not apply in this system. This study provides guidance for understanding important features of pincer ligands with first-transition-row metals that differ from those in heavier metal complexes.

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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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Annelation of furan rings to arenes

Benzo[b]furans have been used in various fields of chemistry and technology due to their unique physical, chemical and biological properties. It is primarily a wide range of biological activities of natural and synthetic benzo[b]furan derivatives and their polyfused analogues (naphthofurans, anthrafurans, etc.) that attracts a significant scientific interest in the context of using these heterocycles as privileged scaffolds in drug design. This survey covers those methods for the annelation of a furan ring to arenes that have been developed mostly during the last decade. We also analyze trends in synthetic methods of benzo[b]furans. Some synthetic schemes are highly efficient in the synthesis of polyfunctionalized furan derivatives. The bibliography includes 110 references.

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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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Herbicidal method

The invention relates to a method for the control of weeds (i.e. undesired vegetation) at a locus, which method comprises applying thereto a herbicidally effective amount of at least one compound which is a 3,5-dicyanophenoxy derivative of formula (I): 1wherein A is as defined in the description; to novel 3,5-dicyanophenoxy derivatives, to new herbicidal compositions containing them, and to processes and intermediates for their preparation.

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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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ESR study of paramagnetic derivatives of sterically hindered di-o-quinone with the tetrathiafulvalene bridge

The paramagnetic derivatives of 4,4?,7,7?-tetra-tert-butyl-2, 2?-bis-1,3-benzodithiol-5,5?,6,6?-tetraone (1), viz., radical anion salts of the alkali metals (Li, Na, K) and cobaltocenium cations, chelated mono-o-semiquinone complexes with different metal fragments (Tl, TlMe 2, SnPh3, Mn(CO)4, Mn(PPh3)(CO) 3), a number of copper(I) complexes with sterically hindered phosphines as well as binuclear heterometallic derivatives of triphenylantimony(V) o-semiquinone-catecholate with the analogous paramagnetic centers, were studied by ESR spectroscopy. The reaction of di-o-quinone 1 with sodium amalgam resulted in the formation of all reduced forms including quinone-semiquinone, disemiquinone, semiquinone-catecholate, and dicatecholate. A radical cation with the unpaired electron localized on the tetrathiafulvalene (TTF) fragment, which resulted from the oxidation of di-o-quinone 1, was detected by ESR spectroscopy.

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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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Rhodium-Catalyzed Synthesis of Organosulfur Compounds using Sulfur

Sulfur is one of the few elements that occurs uncombined in nature. Sulfur atoms are found in natural amino acids and vitamins. In the chemical industry, organosulfur compounds are used for fabricating rubber, fibers, and dyes, pharmaceuticals, and pesticides. Although sulfur, which is cheap and easy to handle, is a useful source of sulfur atom in functional organosulfur compounds, it is rarely used in organic synthesis. Activation of sulfur by high temperature, light irradiation, treatment with nucleophiles and electrophiles, and redox conditions often results in the formation of various active sulfur species, which complicate reactions. The development of a method that mildly activates sulfur is therefore desired. The use of transition-metal catalysts is a new method of activating sulfur under mild conditions, and, in this article, we describe the rhodium-catalyzed synthesis of various organosulfur compounds by the insertion of sulfur atoms into single bonds and by the addition of sulfur to unsaturated bond in various organic compounds. 1 Introduction 2 Sulfur Activation without using Transition Metal 3 Transition-Metal-Catalyzed Activation of Sulfur 4 Rhodium-Catalyzed Reactions using Sulfur 4.1 Rhodium-Catalyzed Sulfur Atom Exchange Reactions using Sulfur 4.2 Synthesis of Diaryl Sulfides using Rhodium-Catalyzed Exchange Reaction of Aryl Fluorides and Sulfur/Organopolysulfides 4.3 Rhodium-Catalyzed Synthesis of Isothiocyanate using Sulfur 4.4 Rhodium-Catalyzed Sulfur Addition Reaction to Alkenes for Thiiranes Synthesis 4.5 Rhodium-Catalyzed Sulfur Addition Reaction to Alkynes for 1,4-Dithiins Synthesis 5 Conclusion.

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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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Thermoregulated phase transfer ligands and catalysis IX. Hydroformylation of higher olefins in organic monophase catalytic system based on the concept of critical solution temperature of the nonionic tensioactive phosphine ligand

Application of the concept of critical solution temperature (CST) of nonionic tensioactive phosphine ligand P[pC6H4O(CH2CH2O)(n)H]3 (PETPP) in the hydroformylation of higher olefins in organic monophase system is presented for the first time. The PETPP/Rh complex catalyst is insoluble in organic solvent at room temperature (T < CST), on heating to the temperature T > CST, the catalyst would be soluble in organic solvent. Thus, the catalytic reaction would have taken place homogeneously at the reaction temperature (T > CST). When the reaction is completed, on cooling to the room temperature (T < CST), the catalyst would precipitate out from the organic solvent, and could be easily separated from the product and recycled efficiently. Hydroformylation of higher olefins catalyzed by PETPP/Rh complex in organic monophase system is investigated. Under the conditions of T = 130C, P = 4.0 MPa, the conversion of 1-dodecene and yield of the aldehyde are 95.8% and 93.7%, respectively.] (C) 2000 Elsevier Science B.V. I hope this article can help some friends in scientific research. I am very proud of our efforts over the past few months and hope to 224311-51-7, help many people in the next few years., Reference of 224311-51-7

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