10150-27-3

Usage

Reaction

Catalyst used for the room temperature cross-coupling of organozinc reagents with carboxylic fluorides, chlorides, anhydrides and thioesters.

Upstream product

• 100-69-6 2-vinylpyridine 
• 829-85-6 diphenylphosphane 
• 1121-60-4 pyridine-2-carbaldehyde 
• 678187-53-6 (tert-butyldimethylsilyl)diphenylphosphine 

Downstream Products

• 113706-02-8 cis-{rhodium(1-(2-pyridyl)-2-(diphenylphosphino)ethane)2}PF₆ 
• 71803-68-4 RhCl(CO)(P(C₆H₅)2C₂H₄(C₅H₄N))2 
• 113705-97-8 trans-{iridium(1-(2-pyridyl)-2-(diphenylphosphino)ethane)2(CO)}PF₆ 
• 113705-93-4 trans-{iridium(1-(2-pyridyl)-2-(diphenylphosphino)ethane)2(CO)Cl} 
• 113705-94-5 {iridium(1-(2-pyridyl)-2-(diphenylphosphino)ethane)(CO)Cl} 
• 113706-04-0 {rhodium(1-(2-pyridyl)-2-(diphenylphosphino)ethane)2(CO)}PF₆ 
• 952587-93-8 (η⁶-C6Me6)Ru(η³-CH2CHCHCHO)Cl 
• 15685-41-3 [2-(2-(diphenylphosphino)ethyl)pyridine]nickel(II) chloride 
• 1594113-15-1 cis-[2-(2-(diphenylphosphino)ethyl)pyridine](2-methylphenyl)nickel(II) chloride 
• 25898-97-9 α-<2-(diphenylphosphinyl)ethyl>pyridine 
• 53080-45-8 dichloro[2-(β-diphenylphosphinoethyl)pyridine]palladium(II) 

Relevant academic research and scientific papers

Valorization of furfural using ruthenium (II) complexes containing phosphorus-nitrogen ligands under homogeneous transfer hydrogen condition

In this paper, we report the catalytic activity of a series of ruthenium (II) complexes containing phosphorus-nitrogen bidentated (P-N) ligands in the hydrogenation of furfural via hydrogen transfer reaction using two hydrogen donor sources: 2-propanol in basic medium and formic acid under mild conditions. The results showed that all the ruthenium complexes studied are catalytically active in the hydrogenation of furfural by hydrogen transfer reaction; they showed 100% conversion with both hydrogen sources. However, selectivities towards the formation of furfuryl alcohol were better when formic acid was used. It was also found that the reaction studied in a basic medium competes with the Cannizzaro reaction, obtaining furfuryl alcohol and furoic acid in a 70/30 ratio; on the other hand, using formic acid as the hydrogen source yields furfuryl alcohol with 100% selectivity. Although formic acid can be used as a hydrogen source successfully. The optimal substrate/acid ratio was found to be 1:1, as a higher concentration of formic acid can cause catalyst decomposition. The yielded products, furfuryl alcohol and furoic acid, obtained from renewable sources, have multiple applications in the organic chemical industry, replacing or complementing similar fossil-derived products.

Photocatalytic Hydrophosphination of Alkenes and Alkynes Using Diphenylphosphine and Triamidoamine-Supported Zirconium

Reactions of alkene or alkyne with diphenylphosphine and catalytic [κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr (1) are greatly enhanced under photolysis, providing viable catalytic hydrophosphination with a broad substrate scope. Whereas diphenylphosphine had been an inaccessible substrate under thermal conditions, complete conversion of alkene substrates to tertiary phosphine is achieved in as little as four hours at ambient temperature with 1 under ultraviolet irradiation. Previously inactive alkenes are now hydrophosphination substrates with diphenylphosphine to produce tertiary phosphine ligands possessing tunable steric and electronic properties.

Catalytic hydrophosphination of styrenes

(equation presented) The first example of intermolecular hydrophosphination of styrenes catalyzed by Ni and Pd complexes is described. The reaction of Ph2PH with styrene, 4-vinylpyridine, 2-vinylpyridine, 4-methoxystyrene, 2-methoxystyrene, and 5-vinyl-2-methylpyridine in benzene under Ni[P(OEt)3]4 catalysis proceeds with high yield and selectivity to give only anti-Markovnikov product.

t-BuOK-catalyzed addition phosphines to functionalized alkenes: A convenient synthesis of polyfunctional phosphine derivatives

The use of t-BuOK in DMSO allows a smooth addition of Ph2PH, Cy2PH and Ph2P(O)H to various functionalized alkenes leading to polyfunctional phosphines in good yields. This method has been used to prepare precursors for P,P- and P,N-ligands.

A Functionalized Alkyldiphenylphosphine as an Efficient and Mild Reagent in CCl4-Promoted Substitution Reactions: Kinetics and Mechanism of the Reaction in CHCl3

(Pyrid-2-ylethyl)diphenylphosphine can be used at 35-45 deg C in carbon tetrachloride-chloroform to give high yields of primary and secondary alkyl chlorides from the corresponding alcohols. The isolation of products is simplified by removal of the phosphorus-containing products by extraction into a dilute aqueous acid solution.The complex reaction was studied by 31P NMR.The rate constants based on the decay of phosphine are reported.The rapid conversion of alcohols proceeds equally via chlorination by CCl3 (path A) and by Cl (path B).The rates of formation and decay of an isobutoxyphosphonium intermediate, Cl, have been measured with 31P NMR.

Visible Light Photocatalysis Using a Commercially Available Iron Compound

[CpFe(CO)2]2 (1) (Cp = η5-C5H5) is an effective precatalyst for the hydrophosphination of alkenes with Ph2PH under visible light irradiation, which appears to be a unique way to promote metal-catalyzed hydrophosphination. Additionally, 1 is a photocatalyst for the dehydrogenation of amine boranes and formation of siloxanes from tertiary silanes. These reactions have similar, if not improved, reactivity over the same transformations using 1 or related CpFeMe(CO)2 under UV irradiation, consistent with the notion that hydrophosphination with 1 proceeds via formation of CpFe(CO)2?. These results demonstrate that catalyst selection can avail the use of commercially available LED bulbs as photon sources, potentially replacing mercury arc lamps or other energy intensive processes in known or new catalytic reactions.

Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex

Herein we report the synthesis of three heteroleptic first-row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)-carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt-catalysed hydrophosphination process that solely and selectively yields the β addition (anti-Markovnikov) product. The scope of this transformation has been investigated using a variety of activated alkenes. Isolation and characterisation of substrate-coordinated intermediates reveal available coordination sites, which provide insight into the proposed catalytic cycle. (Figure presented.).

Neutral and Cationic Zirconium Complexes Bearing Multidentate Aminophenolato Ligands for Hydrophosphination Reactions of Alkenes and Heterocumulenes

Zirconium complexes supported by multidentate aminophenolato ligands were synthesized and characterized. The catalytic activities of neutral zirconium complexes and their cationic derivatives in the hydrophosphination of alkenes as well as heterocumulenes have been investigated and compared. Neutral complex 1 bearing a multidentate amino mono(phenolato) ligand exhibited high activity in hydrophosphination of simple alkenes, and anti-Markovnikov products were obtained in 37-94% yields at room temperature. Cationic species generated in situ from complex 3 stabilized by a bis(phenolato) ligand were found to be more active for hydrophosphination of heterocumulenes, i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67-93% yields. The Lewis acidity and coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.

Iron catalysis for the synthesis of ligands: Exploring the products of hydrophosphination as ligands in cross-coupling

Catalytic hydrophosphination is a useful technique for the synthesis of phosphines, however, the phosphine products have been little exploited as ligands in catalysis. We have selected three phosphines prepared by iron catalyzed hydrophosphination and used them as ligands in a series of cross-coupling reactions: Heck, Suzuki-Miyaura and Buchwald-Hartwig. Rather than limit the chemistry to simple cross-coupling partners which are almost guaranteed to perform well in these transformations, industrially relevant substrates which are challenging from and electronic and/or steric perspective, along with substrates which contain several heteroatoms, were explored in order to gauge the true potential of these phosphine ligands.

Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes

The hydrophosphination of carbon-carbon multiple bonds has been generally performed under acid, base or metal catalysis in different solvents. Herein, alkyl and alkenyl tertiary phosphines are obtained by the addition of diphenylphosphine to alkenes and alkynes, respectively, in the absence of a solvent and a catalyst. In the presence of elemental sulfur, the corresponding alkyl and alkenyl tertiary phosphine sulfides are synthesized in a three-component process. These simple methods, which meet most of the principles of Green Chemistry, are highly regioselective towards the anti-Markovnikov products and diastereoselective towards the Z alkenyl phosphines. The mechanistic aspects of the reactions are also tackled and the efficiency of the latter is compared with that of the catalytic methods.