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Xanthene ring compound and high-efficiency synthesis and resolution method thereof (by machine translation)

The invention relates to a chemical synthesis technology field, and relates to the technical field of chemical synthesis. After optimization, only simple four steps are needed to efficiently obtain the spirocyclic difluoro intermediate product, and the synthesis method is very simple and convenient in operation, and further amplification is easy to carry out in the process of the synthesis method of the novel oxaspiro ring compound after optimizing, and the method, the method and the device are easy to carry out. In addition, the oxonaphthalene diphenols can be effectively separated by an inexpensive and readily available resolution reagent. (by machine translation)

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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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Cyclotetra((lambda3-phosphazanes) derivant de diamines-1,2. Precurseurs de composes du phosphore dicoordonne

Cyclotetraphosphazanes 2 and 5 obtained from 1,2-diamines are 1,3,2-diazaphosphole oligomers leading to the monomeric form by either thermal equilibrium or by complexing with boron trifluoride.The dicoordinated form stabilized by an orthophenylene ring could explain the reactivity of 4,5-benzo 1,3,2-diazaphosphole 3 with compounds having a mobile hydrogen; these reactions were a 1.2 type addition while butanol led to a 1.1 type addition with complexed 1,3,2-diazaphospholes 4 and 8.

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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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CYCLOPHOSPHORYLATED 2,3-O-ISOPROPYLIDENE-D-TREITES

Reported for the first time are 1,3,2-dioxaphosphepane derivatives of 2,3-O-isopropylidene-D-treite, which are rigid condensed systems.Their conformational analysis was performed.Oxidation reactions involving the phosphepanes prepared were studied.

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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 selective markovnikov addition of hypervalent H-spirophosphoranes to alkynes mediated by palladium acetate: Generality and mechanism

Palladium acetate efficiently catalyzes the addition of an H-spirophosphorane (pinacolato)2PH to alkynes to give Markovnikov addition products highlyselectively. The addition products can be easily converted to the corresponding alkenylphosphonates and phosphonicacids viasimple hydrolysis or thermal decomposition. This new reaction isa general method for the introduction of phosphorus functionality to the internal carbons of terminal alkynes, resolving the problem of the regioselectivity associated with hydrophosphorylation reactions so far reported. Mechanistic studies confirmed that (a) palladium acetate was reduced to metallic palladium by H-spirophosphorane, (b) the P-H bond of H-spirophosphorane could be activated by zero-valent platinum complexes to give the corresponding hydridoplatinum complexes, and (c) an alkenylpalladium species was identified from the reaction of palladium acetate with H- spirophosphorane and diphenylacetylene. These results support a reaction mechanism that palladium acetate was first reduced by H-spirophosphorane to give zero-valent palladium. This zero-valent palladium might insert into the P-H bond of the H-spirophosphorane to give a hydridopalladium species which then added to alkyne via the addition of H-Pd bond to form an alkenylpalladium species with the hydrogen atom added to the terminal carbon of alkynes. Reductive elimination of the alkenylpalladium affords the addition product.

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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 PREPARING PHOSPHORAMIDATE DERIVATIVES OF NUCLEOSIDE COMPOUNDS FOR TREATMENT OF VIRAL INFECTIONS

Processes for the production of nucleoside phosphoramidate compounds having the following Formula I are provided.

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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 of Experiments? as a Method to Optimize Dynamic Disulfide Assemblies: Cages and Functionalizable Macrocycles

Cyclophanes are a venerable class of macrocyclic and cage compounds that often contain unusual conformations, high strain, and unusual properties. However, synthesis of complex, functional derivatives remains difficult due to low functional group tolerance, high dilution, extreme reaction conditions, and sometimes low yields using traditional stepwise synthetic methods. ?Design of experiments? (DOE) is a method employed for the optimization of reaction conditions, and we showcase this approach to generate a dramatic increase in the yield of specific targets from two different self-assembling systems. These examples demonstrate that DOE provides an additional tool in tuning self-assembling, dynamic covalent systems.

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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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Benzylic Newman-Kwart rearrangement of O-azidobenzyl thiocarbamates triggered by phosphines: pseudopericyclic [1,3] shifts via uncoupled concerted mechanisms

A series of O-(o- and p-azido)benzyl thiocarbamates smoothly rearranged in the course of Staudinger imination reactions with tertiary phosphines, giving rise to the respective S-(o- and p-phosphinimino)benzyl thiocarbamates as a result of an oxygen to sulfur migration of the functionalized benzyl group. By contrary, their m-azido isomers did not rearrange under similar conditions. Computational investigations using DFT methods revealed the uncoupled concerted mechanisms of these 1,3-benzyl shifts via polar transition states with pseudopericyclic orbital topologies, with the benzyl group migrating in the plane of the thiocarbamate fragment.

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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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Enthalpy of solution and hydrophobic effects in the water-hexamethylphosphorotriamide-tetrabutylammonium bromide system at 298.15 K

The heat effects of solution of tetrabutylammonium bromide (TBA) in water-hexamethylphosphorotriamide (HMPT) mixed solvents were measured over the whole range of solvent compositions on a variable-temperature isothermic-shell calorimeter. The standard enthalpies of solution of TBA and its transfer from HMPT to HMPT-water mixtures were calculated. The McMillan-Mayer model as used to calculate the electrolyte-HMPT pair interaction coefficient. The state of the Bu4N+ ion in water and water-HMPT mixtures was studied in terms of the clathrate model. The results were compared with literature data on mixtures of water with dimethylformamide, dimethylsulfoxide, and dimethylamine.

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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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ZUR REAKTION VON P(III)AMIDEN MIT ORTHOAMEISENSAEUREESTERCHLORIDEN

Both ester diamide, 2a, as well as diester amide, 2b, derivatives of phosphorous acid react with trichlorobenzodioxole, 1, to form the expected ester amide, 3, in small yields only.The main product is the dioxaphosphole, 4.Likewise, trisdimethylaminophosphine reacts with 1 with formation of the dioxaphosphole, 7.This unexpected reaction may be rationalized by assuming competition between N- and P-“diaryloxymethylenation” of the P(III)amide.A similar competition has been observed in the reaction of orthoformate with bis(dimethylamino)chlorophosphine.

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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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Heterocycles Incorporating a Pentacoordinated, Hypervalent Phosphorus Atom

This chapter presents the synthesis of heterocycles with a hypervalent, pentacoordinated phosphorus atom. It is divided into two sections. The first is devoted to the preparation of pentavalent, pentacoordinated, hypervalent monocyclic phosphoranes, and their selected interconversions. The second section, concerning bicyclic heterocycles, describes the synthesis and reactivity of all kinds of bicyclic phosphoranes. The phenomenon of chirality for this group of organophosphorus derivatives is also briefly 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