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New Vistas in Transmetalation with Discrete ?AgCF3? Species: Implications in Pd-Mediated Trifluoromethylation Reactions

This work describes the employment of discrete ?AgCF3? complexes as efficient transmetalating agents to PdII to surmount overlooked challenges related to the transmetalation step in Pd-catalyzed trifluoromethylation processes. We report the participation of a unique silver ate (Cs)[Ag(CF3)2] complex, under stoichiometric and catalytic conditions, in the unprecedented one-pot formation of PhCF3 using PhI as starting material. Moreover, we show that the transmetalation step, which is often ignored in these transformations, can also determine the success or failure of the coupling process.

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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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Visible Light-Induced Excited-State Transition-Metal Catalysis

In recent years, visible light-induced excited-state transition-metal (TM) (Mn, Co, Cu, and Pd) catalysis has attracted significant attention for the development of various chemical transformations. In contrast to metal/photoredox dual catalysis that uses conventional photosensitizers and TMs cooperatively, photoexcited-state TM catalysis uses a single TM complex as both the photocatalyst (PC) and the cross-coupling catalyst, resulting in more sustainable and efficient reactions. Unlike the outer-sphere mechanism active in conventional photocatalysis, these TM catalysts operate through a photoinduced inner-sphere mechanism in which the substrate?TM interaction is crucial for the bond-breaking or bond-forming steps, making this system an important advance in efficient carbon?carbon (C?C) bond formation reactions. Given the importance of these TM complexes as next-generation PCs with distinct mechanisms, in this review we highlight recent developments in photoexcited TM catalysis for C?C bond formation.

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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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Synthesis of RuCl2(xantphos)L (L = PPh3, P(OPh)3, DMSO) complexes, and their catalytic activity for the addition of carboxylic acids onto olefins

Abstract Readily synthesis of a series of RuCl2(xantphos)L (L = PPh3, P(OPh)3, DMSO) was achieved. Thus, RuCl2(xantphos)PPh3 was synthesised by the reaction of RuCl2(PPh3)3 with xantphos. PPh3 in this complex is easily exchanged with P(OPh)3 and Dimethylsulfoxide (DMSO) to give RuCl2(xantphos){P(OPh)3} and RuCl2(xantphos)(DMSO), respectively.

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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 pi – allyl palladium (II) complex and its preparation method and application (by machine translation)

The present invention provides a novel pi – allyl palladium (II) complex and its preparation method and application. This invention is through [Xantphos] PdI (Ph) and sulphone base joint alkene occurred after inserted into the reaction with the silver salt is generated by the reaction of allyl pi – ionic palladium (II) complex, the complex can be used for catalytic bi alkene compound double-funtionalization reaction, at the same time introduced into the bi alkene molecule C – C and C – O key. The invention is characterized in that: the complex can be realized to the metal catalytic second line alkene compound beta – H to eliminate, competition reaction inhibition of aggregation or the like, so that a single reaction, and the reaction area and solid selective control. (by machine translation)

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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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161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 161265-03-8, Computed Properties of C39H32OP2

Palladium-catalyzed carbonylation of thioacetates and aryl iodides for the synthesis of: S -aryl thioesters

Thioesters were synthesized via palladium-catalyzed carbonylation of thioacetates and aryl iodides. S-Aryl thioacetates coupled with carbon monoxide and aryl iodides to afford the desired S-aryl thioesters in good yields. The reaction showed good functional group tolerance toward fluoro, chloro, ketone, ester, aldehyde, cyano, and nitro groups. The tandem reaction of the direct S-arylation of aryl iodides from potassium thioacetate (KSAc) and subsequent carbonylation of the intermediates S-aryl thioacetates provided S-aryl thioesters in moderate-to-good yields.

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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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Variation of xantphos-based ligands in the palladium-catalyzed reaction of aryl halides with ureas

A series of Xantphos-based ligands containing various substituents in the diphenylphosphino groups were synthesized, and their effect on the product yield and ratio in the palladium-catalyzed arylation of ureas with nonactivated aryl halides was studied. The arylation of urea and phenylurea in the presence of Pd2(dba)3-CHCl3, 3,5-(CF3) 2Xantphos, and Cs2CO3 in dioxane at 100C gave the corresponding N,N?-diarylureas in 62-98% yield.

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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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Visible-Light-Driven, Copper-Catalyzed Decarboxylative C(sp3)?H Alkylation of Glycine and Peptides

Despite a well-developed and growing body of work in Cu catalysis, the potential of Cu to serve as a photocatalyst remains underexplored. Reported herein is the first example of visible-light-induced Cu-catalyzed decarboxylative C(sp3)?H alkylation of glycine for preparing alpha-alkylated unnatural alpha-amino acids. It merits mentioning that the mild conditions and the good functional-group tolerance allow the modification of peptides using this method. The mechanistic studies revealed that a radical?radical coupling pathway is involved in the reaction.

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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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161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 161265-03-8, Formula: C39H32OP2

In-situ oxidation, addition and cyclization reaction of 5,6-diamino-1,10-phenanthroline to construct copper(I)-diimine-diphosphine complexes

Reaction of 5,6-diamino-1,10-phenanthroline (dap), chelating diphosphine ligands, 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene (xantphos) and bis[(2-diphenylphosphino)phenyl] ether (POP) with [Cu(MeCN)4]ClO4 afforded mononuclear [Cu(dap)(PP)]ClO4 (PP = xantphos, 1a; POP, 2a), binuclear [Cu2(mu-pdi)(PP)2](ClO4)2 (pdi = 1,10-phenanthroline-5,6-diimine) (PP = xantphos, 1b; POP, 2b) and [Cu2(mu-ttpd)(xantphos)2](ClO4)2 (1c) (ttpd = 8b,9,18,18a-tetrahydrotetrapyrido[3,2-a:2?,3?-c:3?,2?-h:2?,3?-j]phenazine-8b,18a-diamine) complexes. The ligand pdi with a quinone diimine form in complexes 1b and 2b is suggested to result from an in-situ two-electron oxidation of dap under the catalysis of Cu(I) and is stabilized by the coordination to Cu(I) ion, while the unprecedented ligand ttpd in complex 1c is suggested to originate from the in-situ oxidation, addition and cyclization reaction of dap induced and stabilized by crystallized Cu(I)-diimine-diphosphine complex. The plausible formation mechanisms for the Cu(I) complexes are proposed.

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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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HYDROGENATION OF ESTERS WITH RU/BIDENTATE LIGANDS COMPLEXES

The present invention relates to processes for the reduction by hydrogenation, using molecular H2, of a substrate containing one or two esters, or lactones, functional groups into the corresponding alcohol, or diol, said process is carried out in the presence of a base and at least one catalyst or pre-catalyst in the form of a ruthenium complex wherein the ruthenium is coordinated by a diphosphine bidentate ligand (PP ligand) and a diamino bidentate ligand (NN ligand) comprising at least one substituted alpha-carbon and one primary amine as one of the coordinating atoms.

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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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Ruthenium-Catalyzed C-C bond cleavage in lignin model substrates

Ruthenium-triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox-neutral C-C bond cleavage of the beta-O-4 lignin linkage of 1,3-dilignol model compounds. A mechanistic pathway involving a dehydrogenation-initiated retro-aldol reaction for the C-C bond cleavage was proposed in line with experimental data and DFT calculations.

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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