4877-08-1

Upstream product

• 106-44-5 p-cresol 
• 762-04-9 phosphonic acid diethyl ester 
• 29540-83-8 p-tolyl triflate 
• 54058-00-3 diethyl phosphite potassium salt 
• 1192-96-7 potassium p-cresolate 
• 814-49-3 diethyl chlorophosphate 
• 2942-58-7 diethyl cyanophosphonate 
• 78-40-0 triethyl phosphate 
• 17988-20-4 (4-methoxy-benzyl)-trimethyl-silane 
• 67-56-1 methanol 
• 101224-30-0 4-((trimethylsilyl)methyl)phenol 

Downstream Products

• 195062-57-8 p-tolylboronic pinacol ester 
• 83110-01-4 diethyl 2-hydroxy-5-methylphenyl phosphonate 
• 644-08-6 4-Methylbiphenyl 
• 53040-92-9 4-(4-tolyl)anisole 
• 129529-20-0 2-(Diethyl-phosphinoyl)-4-methyl-phenol 

Relevant academic research and scientific papers

Electrochemical phosphorylation of arenols and anilines leading to organophosphates and phosphoramidates

A practical phosphorylation for generating organophosphates and phosphoramidatesviaelectrochemical dehydrogenative cross-coupling of P(O)H compounds with arenols and anilines is disclosed. This method involves using inorganic iodide salts as both redox catalysts and electrolytes in an undivided cell without the addition of oxidants or bases. A preliminary mechanistic study suggests that radicals are not involved in this process. This method is green and eco-friendly and has good functional group tolerance, high yields and broad substrate scope, with the potential for practical synthesis.

LiI/TBHP Mediated Oxidative Cross-Coupling of P(O)–H Compounds with Phenols and Various Nucleophiles: Direct Access to the Synthesis of Organophosphates

An efficient and mild method for the direct phosphorylation of phenols, alcohols, and amines with P(O)–H has been reported by LiI/TBHP mediated oxidative cross-coupling reaction. Moreover, this protocol extended to β-keto esters for the synthesis of enol phosphates using H-phosphonates. Notably, this developed method applied for the synthesis of organopesticides such as paraoxon, cyanophos, and methyl parathion. The key features of this protocol are mild conditions, short reaction time, good functional group tolerance, and broad substrate scope.

Tf2O-Promoted Activating Strategy of Phosphate Analogues: Synthesis of Mixed Phosphates and Phosphinate

A metal-, toxic chloride reagent-free activating strategy of various phosphates has been developed. This method enables the facile synthesis of functional phosphates such as alkyl phosphates, aza phosphates, thiophosphate, and mixed diaryl phosphates. A transient phosphorylpyridin-1-ium species in situ generated from phosphates with Tf2O/pyridine readily undergoes a substitution reaction with diverse nucleophiles to form versatile phosphate compounds.

Enantioselective and Regioselective Hydroetherification of Alkynes by Gold-Catalyzed Desymmetrization of Prochiral Phenols with P-Stereogenic Centers

The gold(I)-catalyzed enantioselective hydroetherification of alkynes was achieved via desymmetrization of prochiral bisphenols bearing P-stereogenic centers. (S)-DTBM-Segphos(AuCl)2/AgNTf2 proved to be a highly efficient catalyst system for this transformation, affording P-chiral cyclic phosphine oxides in good yields with high enantioselectivities (with up to 99% ee). The same catalyst system allowed for the enantioselective desymmetrization of dialkynes. Synthetic transformations of the cyclization products afforded other P-chiral molecules with high enantiospecificity.

Competing pathways in the photogeneration of didehydrotoluenes from (Trimethylsilylmethyl)aryl sulfonates and phosphates

The scope of the photochemical generation of a,n-didehydrotoluene diradicals from aryl sulfonates and phosphates and their chemistry are explored. The thermally inaccessible a,2- and a,4-intermediates are efficiently obtained by irradiation of ortho- and para-(trimethylsilylme-thyl)phenyl triflates through heterolytic splitting of the ester anion from the substrate in the triplet state. Triplet phenyl cations are formed and the loss of trimethylsilyl cation from them affords the desired diradicals (3Me3SiCH2C6H4-OZ→ 3Me3SiCH2C6H4+→CH2C6H4). Triplet sensitization is required, for which acetone is used throughout. Direct irradiation leads, on the contrary, to photo-Fries fragmentation (1Me3SiCH2C6H4O-Z→Me3SiCH2C6H4O· + Z). With mesylates, where ester cleavage is less convenient, a further competition from the triplet is direct desilylation. Didehydrotoluenes are also obtained from the corresponding phosphates, although with poor efficiency.

Triethylphosphate/phosphorus pentoxide as an efficient reagent for the phosphorylation of phenols

A simple, efficient, and novel method has been developed for the phosphorylation of phenols. Treatment of phenols with a mixture of triethylphosphate/phosphorus pentoxide gives the corresponding phosphate derivatives in good yields. This method is easy, rapid, and offers good yields for the phosphorylation of phenols. The reaction of triethylphosphate with phosphorus pentoxide was also studied by variable-temperature 31P-NMR spectroscopy. Copyright

An improved method for Lewis acid catalyzed phosphoryl transfer with Ti(t-BuO)4

Several inorganic esters have been evaluated as phosphoryl transfer catalysts. Of these, Ti(t-BuO)4 was found to be the most effective catalyst giving excellent yields of the desired phosphate esters. The loading of the catalyst could be reduced to a little as 5 mol % for a majority of substrates with no loss in the yield of product. This methodology is significantly more versatile than using TiCl4 and is suitable for the phosphorylation of more complex carbohydrates and molecules of biological interest.

Phosphorylation of phenols with diethyl chlorophosphonate on the surface of magnesia

Phosphorylation of phenols with diethyl chlorophosphonate on the surface of magnesia is an easy, rapid, safe and high-yielding reaction.

A convenient method for the phosphorylation of phenols with diethyl cyanophosphonate

Phosphorylation of phenols with diethyl cyanophosphonate in methylene chloride solution at 0°C is an easy, rapid and good yielding reaction.