34595-07-8

Upstream product

• 100-47-0 benzonitrile 
• 762-04-9 phosphonic acid diethyl ester 
• 31238-50-3 (2-aminophenyl)phosphonic acid diethyl ester 
• 544-92-3 copper(I) cyanide 
• 151-50-8 potassium cyanide 
• 77526-90-0 diethyl (2-bromobenzyl)phosphonate 
• 611-20-1 salicylonitrile 
• 873-32-5 2-Chlorobenzonitrile 
• 122-52-1 triethyl phosphite 
• 2042-37-7 o-cyanobromobenzene 
• 55305-43-6 N-cyano-N-phenyl-p-toluenesulfonamide 
• 1754-49-0 diethyl phenylphosphonate 
• 13294-40-1 ortho-nitro-phenylphosphonate diethylique 

Downstream Products

• 34595-06-7 diethyl (2-formylphenyl)phosphonate 

Relevant academic research and scientific papers

Sensitization-Initiated Electron Transfer for Photoredox Catalysis

Photosynthetic organisms exploit antenna chromophores to absorb light and transfer excitation energy to the reaction center where redox reactions occur. In contrast, in visible-light chemical photoredox catalysis, a single species (i.e., the photoredox catalyst) absorbs light and performs the redox chemistry. Mimicking the energy flow of the biological model, we report a two-center photoredox catalytic approach in which the tasks of light energy collection and electron transfer (i.e., redox reactions) are assigned to two different molecules. Ru(bpy)3Cl2 absorbs the visible light and transfers the energy to polycyclic aromatic hydrocarbons that enable the redox reactions. This operationally simple sensitization-initiated electron transfer enables the use of arenes that do not absorb visible light, such as anthracene or pyrene, for photoredox applications. We demonstrate the merits of this approach by the reductive activation of chemical bonds with high reduction potentials for carbon–carbon and carbon–heteroatom bond formations.

Direct synthesis of ortho-halogenated arylphosphonates via a three-component reaction involving arynes

A three-component reaction involving arynes, trialkyl phosphites, and halides has been achieved under mild reaction conditions. This transformation provides a direct synthetic approach to ortho-halogenated arylphosphonates, which could be rapidly converted to diversely ortho-functionalized arylphosphorus com ounds

Palladium-catalyzed one-pot phosphorylation of phenols mediated by sulfuryl fluoride

We report a general palladium-catalyzed one-pot procedure for the synthesis of phosphonates, phosphinates and phosphine oxides from phenols mediated by sulfuryl fluoride. It features mild conditions, broad substrate scope, high functionality tolerance and water insensitivity. The utility of this procedure has been well demonstrated by gram-scale synthesis, sequential synthesis of click chemistry building blocks, late-stage decoration of drugs and natural products and on-DNA synthesis of phosphine oxide for a DNA-encoded library (DEL).

peri-Xanthenoxanthene (PXX): a Versatile Organic Photocatalyst in Organic Synthesis

Recent years have witnessed a continuous development of photocatalysts to satisfy the growing demand of photophysical and redox properties in photoredox catalysis, with complex structures or alternative strategies devised to access highly reducing or oxidising systems. We report herein the use of peri-xanthenoxanthene (PXX), a simple and inexpensive dye, as an efficient photocatalyst. Its highly reducing excited state allows activation of a wide range of substrates, thus triggering useful radical reactions. Benchmark transformations such as the addition of organic radicals, generated by photoreduction of organic halides, to radical traps are initially demonstrated. More complex dual catalytic manifolds are also shown to be accessible: the β-arylation of cyclic ketones is successful when using a secondary amine as organocatalyst, while cross-coupling reactions of aryl halides with amines and thiols are obtained when using a Ni co-catalyst. Application to the efficient two-step synthesis of the expensive fluoro-tetrahydro-1H-pyrido[4,3-b]indole, a crucial synthetic intermediate for the investigational drug setipiprant, has been also demonstrated. (Figure presented.).

Visible-Light photo-Arbuzov reaction of aryl bromides and trialkyl phosphites yielding aryl phosphonates

Aryl phosphonates are functional groups frequently found in pharmaceutical and crop protection agents. For their synthesis via C?P bond formation typically transition-metal-catalyzed reactions are used. We report a visible-light photo-Arbuzov reaction as an efficient, mild, and metal-free alternative. Rhodamine 6G (Rh.6G) is used as the photocatalyst, generating aryl radicals under blue light. Coupling of the radicals with a wide range of trivalent phosphites gives aryl phosphonates in good to very good isolated yields. The mild reaction conditions allow the introduction of a phosphonate group into complex and sensitive pharmaceutically active molecules such as benzodiazepams and nicergoline by the activation of a carbon?halogen bond.

Rhodium catalyzed ortho-cyanation of arylphosphates with N-cyano-N-phenyl-p-toluenesulfonamide

A rhodium-catalyzed cyanation of chelation assisted C-H bonds is described. This process provided a useful method for the preparation of diverse 2-cyanated arylphosphonate and related compounds in good yields. The reaction tolerates a variety of synthetic

Manganese(III)-mediated direct phosphonylation of arenes

Manganese (III)-promoted direct phosphonylation of mono- and disubstituted arenes with dialkylphosphite afforded regioselective dialkylphosphonates in good yields. The reactions can apply to arenes bearing electron-donating groups and electron-withdrawing

Oxidative Phoshonylation of Aromatics with Ammonium Cerium(IV) Nitrate

Arylphosphonates 5 and 6 can be prepared in good yields in a one-step synthesis starting from arenes with tri- or diethylphosphites and cerium ammonium nitrate (CAN) as oxidant.The seletivity of the oxidative phosphonylation is relatively low; the reactive species is a phosphite radical cation.

OXIDATIVE PHOSPHONYLATION OF AROMATIC COMPOUNDS

Aryl phosphonates can be prepared in good yield from the respective arenes and tri- or dialkylphosphites by either chemical or anodic oxidation.The anodic oxidation proceeds either via phosphinium radical cations, which then attack the arenes electrophilically, or via arene radical cations, which add the trialkylphosphite as nucleophile.Aryl phosphonates are also obtained in good yield by chemical oxidation with peroxodisulfate/AgNO3 in acetonitrile/water or glacial acetic acid.The diethylphosphinium radical cation, formed from diethylphosphite by oxidation with Ag(II), is supposed to be the reactive species in this process.Raising the silver salt concentration leads to an increase in polyphosphonylation.Selectivity ratios were determined for the oxidative phosphonylation process.