32660-24-5

Upstream product

• 12150-46-8 1,1'-bis-(diphenylphosphino)ferrocene 
• 7732-18-5 water 
• 3375-31-3 palladium diacetate 
• 1072-71-5 2,5-Dimercapto-1,3,4-thiadiazole 
• 98-83-9 isopropenylbenzene 
• 1310-73-2 sodium hydroxide 
• 103-84-4 Acetanilid 
• 7722-84-1 dihydrogen peroxide 

Downstream Products

• 244181-28-0 (C₆H₅)2P(O)C₅H₄FeC₅H₄P(O)(C₆H₅)2PdCl₂ 
• 352196-34-0 [Ag(I)(OClO₃)(1,1'-bis(diphenyloxophosphoryl)ferrocene)] 
• 352196-38-4 [Ag(I)(1,1'-bis(diphenyloxophosphoryl)ferrocene)(PPh₃)]ClO₄ 
• 511243-15-5 [Co(1,1'-bis(diphenylphosphoranyl)ferrocene)I₂]*CH₂Cl₂ 

Relevant academic research and scientific papers

Air-stable phosphine organocatalysts for the hydroarsination reaction

Readily-available triarylphosphines are explored as organocatalysts for the hydroarsination reaction. When compared to transition metal catalysis, phosphine organocatalysis greatly improved solvent compatibility of the hydroarsination of nitrostyrenes. Upon complete conversion, arsine products were isolated in up to 99% yield while up to 48% of the phosphine catalyst was still active. A mechanism was proposed and structure-activity analysis regarding catalyst activity concluded that sterically-bulkier catalysts were effective at minimizing catalyst deactivation.

Lanthanide nitrate complexes of the redox active ligand (η5C5H4P(O)Ph2)2Fe

The synthesis of complexes of (η5C5H4P(O)Ph2)2Fe = L with lanthanide nitrates is described. The single crystal X-ray structures for La(NO3)3L(μ-L)La(NO3)3L

Role of dppf Monoxide in the Transmetalation Step of the Suzuki-Miyaura Coupling Reaction

Diphosphine ligands are frequently used in palladium-catalyzed Suzuki-Miyaura (S-M) reactions. Despite their widespread application in both academic and industrial settings, their role in the B-to-Pd transmetalation has not been firmly established. We combined electrochemistry, NMR spectroscopy, and DFT calculations to elucidate the role of dppf (1,1′-bis(diphenylphosphino)ferrocene) in this key elementary step of the S-M reaction. We observed that excess dppf inhibits transmetalation involving PhB(OH)2 and dppf-ligated arylpalladium(II) complexes, while an optimal [base]/[PhB(OH)2] ratio maximizes the concentration of a [Pd-O-B] key intermediate. In situ oxidation of dppf to the diphosphine monoxide dppfO can take place in the presence of base, leading to dppfO-ligated arylpalladium(II) complexes, which readily undergo transmetalation at room temperature. These findings suggest guidelines for the rational optimization of diphosphine-promoted S-M reactions.

Radical C-H Arylation of Oxazoles with Aryl Iodides: Dppf as an Electron-Transfer Mediator for Cs2CO3

A radical C-H arylation reaction of oxazoles with (hetero)aryl iodides using Cs2CO3 as base/electron donor and 1,1′-bis(diphenylphosphino) ferrocene (dppf) as a catalytic SET mediator is reported. The overall reaction likely follows the general base-promoted homolytic aromatic substitution mechanism through a radical-chain pathway. DFT calculations suggest that dppf forms a complex with CsCO3-, enhancing its SET reducing ability to generate an aryl radical from ArI.

Thiyl radical promoted chemo- and regioselective oxidation of CC bonds using molecular oxygen: Via iron catalysis

The first example of the thiyl radical promoted ligand-free iron-catalyzed oxidative cleavage of alkenes using molecular oxygen (1 atm) has been developed. The reaction proceeds under mild reaction conditions with high efficiency and high chemo- and regioselectivity. It features a broad substrate scope and excellent functional group compatibility, enabling facile access to valuable molecules for application in medicinal chemistry. Preliminary mechanistic studies reveal that a vital intermediate dioxetane might be involved in the reaction and a thiyl radical plays a synergistic role in facilitating the selective oxidation of the CC bond.

Chemoselective Reduction of Phosphine Oxides by 1,3-Diphenyl-Disiloxane

Reduction of phosphine oxides to the corresponding phosphines represents the most straightforward method to prepare these valuable reagents. However, existing methods to reduce phosphine oxides suffer from inadequate chemoselectivity due to the strength of the P=O bond and/or poor atom economy. Herein, we report the discovery of the most powerful chemoselective reductant for this transformation to date, 1,3-diphenyl-disiloxane (DPDS). Additive-free DPDS selectively reduces both secondary and tertiary phosphine oxides with retention of configuration even in the presence of aldehyde, nitro, ester, α,β-unsaturated carbonyls, azocarboxylates, and cyano functional groups. Arrhenius analysis indicates that the activation barrier for reduction by DPDS is significantly lower than any previously calculated silane reduction system. Inclusion of a catalytic Br?nsted acid further reduced the activation barrier and led to the first silane-mediated reduction of acyclic phosphine oxides at room temperature.

Dehydrative glycosylation with cyclic phosphonium anhydrides

Cyclic phosphonium anhydrides generated from bis-phosphine oxides and trifluoromethanesulfonic anhydride are shown as general coupling reagents in a dehydrative glycosylation reaction of C1-hemiacetals. This reaction protocol is characterized by a broad substrate scope and high yields, including reactions of O-, C-, N-, and S-based nucleophiles with furanose, pyranose, and deoxysugar donors.

Synthesis, characterization and properties of copper(I) complexes with bis(diphenylphosphino)-ferrocene ancillary ligand

Three copper(I) complexes (2-4) containing dppf ancillary ligand (dppf = bis(diphenylphosphino)-ferrocene) were synthesized when chloride-bridged copper(I) complex 1 reacted with acetanilide and characterized by IR, element analysis and NMR spectrum. And the crystal structures of complexes 2 and 4 have been determined by X-ray diffraction method. Complex 2, an acetate-bridged copper(I) complex, was obtained under N2 atmosphere in un-dried solvent; the acetate ion came from the hydrolysis reaction of acetanilide due to residual water in solvent. Acetanilide was deprotonated and coordinated with the copper(I) centre to form a copper(I) amidate complex 3 when reacted in pre-dried solvent. In addition, a known complex 4, the oxidation product of dppf, was isolated from the same reaction system when reacted in air atmosphere. CV and TG experiments were carried out to check the electron transfer properties and thermal stabilities of complexes 2-3. Finally, the arylation reaction of complex 3 with iodobenzene was performed to study the reaction mechanism of copper(I) catalyzed Goldberg reaction.

Acceptor-substituted ferrocenium salts as strong, single-electron oxidants: Synthesis, electrochemistry, theoretical investigations, and initial synthetic application

A series of mono- and 1,1'-diheteroatom-substituted ferrocene derivatives as well as acylated ferrocenes was prepared efficiently by a unified strategy that consists of selective mono- and 1,1'-dilithiation reactions and subsequent coupling with carbon, phosphorus, sulfur and halogen electrophiles. Chemical oxidation of the ferrocene derivatives by benzoquinone, 2,3-dichloro-5,6- dicyanobenzoquinone, AgPF6, or 2,2,6,6-tetramethyl-1-oxopiperidinium hexafluorophosphate provided the corresponding ferrocenium salts. The redox potentials of the synthesized ferrocenes were determined by cyclic voltammetry, and it was observed that all new ferrocenium salts have stronger oxidizing properties than standard ferrocenium hexafluorophosphate. An initial application of selected derivatives in an oxidative bicyclization revealed that they mediate the transformation under considerably milder conditions than ferrocenium hexafluorophosphate. Quantum chemical calculations of the reduction potentials of the substituted ferrocenium ions were carried out by using a standard thermodynamic cycle that involved the gas-phase energetics and solvation energies of the contributing species. A remarkable agreement between theory and experiment was found: the mean average deviation amounted to only 0.030-V and the maximum deviation to 0.1-V. This enabled the analysis of various physical contributions to the computed reduction potentials of these ferrocene derivatives, thereby providing insight into their electronic structure and physicochemical properties. Copyright

Synthesis and structure of lanthanide complexes with large-bite diphosphine dioxide ligands

Three large-bite diphosphine dioxide ligands were reacted with lanthanide salts to yield either molecular or polymeric complexes. The two flexible ligands gave bischelate complexes of general formulae [Ln(dppfO2) 2Clx(NOs