15286-19-8

Upstream product

• 104-92-7 1-bromo-4-methoxy-benzene 
• 868-85-9 Dimethyl phosphite 
• 3471-32-7 4-Methoxyphenylhydrazine 
• 121-45-9 phosphorous acid trimethyl ester 
• 66107-29-7 4-methoxyphenyl triflate 
• 150-76-5 4-methoxy-phenol 
• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 696-62-8 para-iodoanisole 
• 623-12-1 4-chloromethoxybenzene 
• 5720-07-0 4-methoxyphenylboronic acid 
• 104-94-9 4-methoxy-aniline 
• 100-66-3 methoxybenzene 
• 19909-85-4 dichloro-4-methoxyphenylphosphine 
• 19909-83-2 p-Methoxy-phenyl-phosphonigsaeure-dimethylester 

Downstream Products

• 54844-84-7 (p-methoxyphenyl)dimethylphosphine oxide 
• 21778-19-8 (4-methoxyphenyl)phosphonic acid 

Relevant academic research and scientific papers

C-P bond formation of cyclophanyl-, and aryl halides: Via a UV-induced photo Arbuzov reaction: A versatile portal to phosphonate-grafted scaffolds

A new versatile method for the C-P bond formation of (hetero)aryl halides with trimethyl phosphite via a UV-induced photo-Arbuzov reaction, accessing diverse phosphonate-grafted arenes, heteroarenes and co-facially stacked cyclophanes under mild reaction

Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides

Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN?-*, which can be used to activate reductively recalcitrant aryl chlorides (Ered ≈ -1.9 to -2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.

Cobalt catalyzed C-P bond formation by cross-coupling of boronic acids with P(O)H compounds in presence of zinc

In our current work, we have reported the first cobalt-catalyzed cross-coupling of arylboronic acid with alkyl/aryl phosphites under mild conditions. The reaction was carried out in the presence of zinc powder as an additive and ter-pyridine as a ligand. The use of non-precious cobalt salt makes the protocol advantageous, as it is inexpensive and more abundant than the previously used methods where precious metal salts (Pd and Pt) were used. The reaction has a wide substrate scope and the products were obtained in good yields.

Photoinduced Transition-Metal-Free Cross-Coupling of Aryl Halides with H-Phosphonates

Photoinduced transition-metal- and photosensitizer-free cross-coupling of aryl halides (including Ar-Cl, Ar-Br, and Ar-I) with H-phosphonates (including dialkyl phosphonates and diarylphosphine oxides) is reported. Various functional groups were tolerated, including ester, methoxy, dimethoxy, alkyl, phenyl, trifluoromethyl, and heterocyclic compounds. This simple and green strategy provides a practical pathway to synthesize arylphosphine oxides.

A mild electroassisted synthesis of (hetero)arylphosphonates

The electrochemically-assisted synthesis of (hetero)arylphosphonates from (hetero)aryl halides and dimethyl phosphite is described. Very mild and simple conditions are employed as the cross-coupling is carried out in galvanostatic mode, in an undivided ce

Metal-Free Aromatic Carbon-Phosphorus Bond Formation via a Sandmeyer-Type Reaction

An efficient metal-free phosphorylation process based on a Sandmeyer-type transformation with arylamines as the starting materials is developed. The transformation proceeds smoothly at room temperature without the exclusion of moisture or air. This phosphorylation reaction tolerates a wide range of functional groups and affords the phosphorylation products in moderate to good yields, thus providing a valuable method for the formation of aromatic carbon-phosphorus bonds.

A dual catalytic strategy for carbon-phosphorus cross-coupling via gold and photoredox catalysis

A new method for the P-arylation of aryldiazonium salts with H-phosphonates via dual gold and photoredox catalysis is described. The reaction proceeds smoothly at room temperature in the absence of base and/or additives, and offers an efficient approach t

Copper-catalyzed coupling reaction of arylhydrazines and trialkylphosphites

A novel CuO-catalyzed coupling reaction of arylhydrazines with trialkyl phosphites to afford arylphosphonates is described. The reaction proceeded at 80 C in air without external reductants, oxidants, and ligands.

Direct conversion of phosphonates to phosphine oxides: An improved synthetic route to phosphines including the first synthesis of methyl JohnPhos

The synthesis of tertiary phosphine oxides from phosphonates was achieved reliably and in good to excellent yields using stoichiometric amounts of alkyl or aryl Grignard reagents and sodium trifluoromethanesulfonate (NaOTf). In the absence of the NaOTf additive, covalent coordination oligomers of magnesium and phosphorus species dominate the reaction, producing very low yields of phosphine oxide, but high conversions of the phosphonate starting material. Mechanistic studies revealed that a five-coordinate phosphorus species - not a phosphinate - is the reaction intermediate. A diverse array of phosphonates was converted to phosphine oxides using a variety of Grignard reagents for direct carbon-phosphorus functionalization. This new methodology especially simplifies the synthesis of dimethylphosphino (RPMe2)-type phosphines by using air-, water-, and silica-stable intermediates. To highlight this reaction, a new Buchwald-type ligand ([1,1′-biphenyl]-2-yldimethylphosphine, or methyl JohnPhos) and a classic bidentate phosphine, bis(diphenylphosphino)propane (dppp), were synthesized in excellent yields.

A facile route to vinyl- and arylphosphonates by vinyl and aryl radical trapping with (MeO)3P

The generation of vinyl or aryl radicals under classical, thermal AIBN/n-Bu3SnH conditions at 80 °C in the presence of an excess of (MeO)3P gives rise to the corresponding vinyl- or arylphosphonates in good yields. This approach comp