15286-17-6

Upstream product

• 529-28-2 4-iodoanisol 
• 122-52-1 triethyl phosphite 
• 762-04-9 Diethyl phosphonate 
• 59099-58-0 2-methoxyphenyl triflate 
• 100-66-3 methoxybenzene 
• 762-04-9 phosphonic acid diethyl ester 
• 578-57-4 2-bromoanisole 
• 69646-14-6 (2-hydroxy-phenyl)-phosphonic acid diethyl ester 
• 74-88-4 methyl iodide 
• 89620-99-5 silver diethyl phosphonate 
• 579-75-9 2-Methoxybenzoic acid 
• 5720-06-9 2-Methoxyphenylboronic acid 
• 90-04-0 2-methoxy-phenylamine 
• 90-05-1 2-methoxy-phenol 

Downstream Products

• 7506-85-6 2-methoxyphenylphosphonic acid 
• 53839-05-7 o-anisylphosphonic dichloride 
• 126590-38-3 (2-methoxyphenyl)phosphine 
• 1451210-93-7 (E)-butyl 3-(2-(diethoxyphosphoryl)-3-methoxyphenyl)acrylate 
• 1219977-99-7 (2-methoxyphenyl)phosphonic acid monoethyl ester 
• 1605306-43-1 C₁₂H₁₆NO₄P 

Relevant academic research and scientific papers

A Duality of Mechanism in the Hydrolysis of Acyclic Phosphoranes

Acyclic phosphoranes, ArnP(OR)5-n with n=0-3 are shown to hydrolyse in neutral conditions by SN1 (P) mechanism for n=1,2, and 3 but by an SN2 (P) or addition-elimination mechanism for n=0; this is analogous to the classical SN1 vs.SN2 mechanisms observed for solvolysis reactions at tetrahedral carbon.

Development of a room temperature Hirao reaction

Arylphosphonates were prepared at 25 °C through the palladium-catalyzed coupling of aryl iodides with a silver phosphonate. A wide range of aryl iodides were successfully employed including phenolic substrates as well as those containing an ortho substitu

Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine

In this work, we developed a ligand- and base-free visible-light-mediated protocol for the photoredox syntheses of arylphosphonates and, for the first time, alkyl phosphonates. Zinc phthalocyanine-photocatalyzed Csp2-P and Csp3-P bond formations were efficiently achieved by reacting aryl/alkylhydrazines with trialkylphosphites in the presence of air serving as an abundant oxidant. The reaction conditions tolerated a wide variety of functional groups.

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).

Photoinduced transition-metal and external photosensitizer free cross-coupling of aryl triflates with trialkyl phosphites

Photoinduced phosphonation of aryl triflates with trialkyl phosphites via a tandem single-electron-transfer, C-O bond cleavage and Arbuzov rearrangement process in the absence of transition-metal and external photosensitizer is reported herein. The protoc

Arylphosphonate-Directed Ortho C-H Borylation: Rapid Entry into Highly-Substituted Phosphoarenes

Phosphonate-directed ortho C-H borylation of aromatic phosphonates is reported. Using simple starting materials and commercially accessible catalysts, this method provides steady access to o-phosphonate arylboronic esters bearing pendant functionality and flexible substitution patterns. These products serve as flexible precursors for a variety of highly substituted phosphoarenes, and in situ downstream functionalization of the products is described.

Decarbonylative Phosphorylation of Carboxylic Acids via Redox-Neutral Palladium Catalysis

We describe the direct synthesis of organophosphorus compounds from ubiquitous aryl and vinyl carboxylic acids via decarbonylative palladium catalysis. The catalytic system shows excellent scope and tolerates a wide range of functional groups (>50 examples). The utility of this powerful methodology is highlighted in the late-stage derivatization directly exploiting the presence of the prevalent carboxylic acid functional group. DFT studies provided insight into the origin of high bond activation selectivity and P(O)-H isomerization pathway.

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.

Cu2O/TiO2 nanoparticles as visible light photocatalysts concerning C(sp2)-P bond formation

A novel and efficient method has been developed for the construction of an aromatic-phosphorus (Ar-P) bond under visible light irradiation using Cu2O/TiO2 nanoparticles as inexpensive and available photocatalysts. This protocol is a simple system without the use of any base, ligand, oxidant, or special conditions. This is the first report for the synthesis of arylphosphonates from arylhydrazines in visible light irradiation.

Visible-Light-Mediated Metal-Free Synthesis of Aryl Phosphonates: Synthetic and Mechanistic Investigations

This work describes a straightforward access to a large variety of aryl phosphonates by the simple combination of diaryliodonium salts with phosphites in the presence of a base and under visible-light illumination. The reaction proceeds smoothly, tolerates various functionalities, and was applied for the synthesis of pharmaceutically relevant compounds. Mechanistic investigations, including EPR, NMR, and DFT calculations, support the postulated reaction mechanism.