20408-33-7

Upstream product

• 14467-94-8 diethyl <(trimethylsilyl)methyl>phosphonate 
• 100-52-7 benzaldehyde 
• 1660-94-2 Tetraethyl methylenediphosphonate 
• 588-72-7 [(E)-2-bromoethenyl]benzene 
• 17911-19-2 (2-Phenyl-1-trimethylsilyloxyethan)-phosphonsaeurediethylester 
• 95601-03-9 [1-(diethoxyphosphoryl)-2-phenyl-vinyl]-phosphonic acid diethyl ester 
• 75-77-4 chloro-trimethyl-silane 
• 87762-64-9 O,O-diethyl bismethylphosphonate 
• 683-08-9 Diethyl methylphosphonate 
• 116800-91-0 C₉H₂₁O₆P₂^(1-) 
• 814-49-3 diethyl chlorophosphate 
• 591-50-4 iodobenzene 
• 682-30-4 Diethyl vinylphosphonate 
• 536-74-3 phenylacetylene 

Downstream Products

• 54553-21-8 diethyl 2-phenylethylphosphonate 
• 97006-83-2 (1,2-Dihydroxy-2-phenyl-ethyl)-phosphonic acid diethyl ester 
• 60096-50-6 (S)-N-Nitroso-O-methylprolinol 
• 213193-36-3 {2-Hydroxy-3,3-dimethyl-1-[1-phenyl-meth-(E)-ylidene]-butyl}-phosphonic acid diethyl ester 
• 6324-00-1 1-amino-2-phenylethanephosphonic acid 
• 182207-52-9 (2R,4S,5R)-5-[(tert-butoxycarbonyl)amino]-2-ethoxy-4-phenyl-2-oxo-1,2-oxaphosphorinane 

Relevant academic research and scientific papers

Mechanistic insight into the copper-catalyzed phosphorylation of terminal alkynes: A combined theoretical and experimental study

The reaction mechanism of copper-catalyzed phosphorylation of terminal alkynes under different conditions has been investigated experimentally and theoretically. The important role of dioxygen has been elucidated, including the formation of η1-superoxocopper(II), η2- superoxocopper(III), μ-η2:η2-peroxodicopper(II) , and bis(μ-oxo)dicopper(III) complexes. More importantly, the proton transfer from the dialkyl phosphonate (in the form of phosphite) to the bridging oxygen atom entails the migration of the deprotonated phosphonate to the terminal alkyne, leading to the formation of a C-P bond with an activation barrier of only 1.8 kcal/mol. In addition, a particularly stable six-centered dicopper(I) species is formed with the migration of both of the Ph 2P(O) groups from the copper atoms to the oxygen atoms of the bis(μ-oxo) bridge, explaining the experimental observation that secondary phosphine oxides can be oxidized to the phosphinic acids. Thus, the diphenylphosphine oxide was added to the reaction mixture dropwise to minimize the concentration during the reaction course. Gratifyingly, the coupling product was generated almost quantitatively when the reaction was completed.

Hydrophosphorylation of terminal alkynes catalyzed by palladium

A series of new 1-aryl-, 1-heteroaryl-, and 1-alkylethenylphosphonates was prepared by hydrophosphorylation of terminal acetylenes catalyzed by palladium. A stable in air complex Pd2(dba)3·CHCl3 was applied as catalyst. The reaction mechanism is discussed.

Stereoselective synthesis of vinylphosphonate

Dialkyl vinylphosphonate is stereoselectively prepared by palladium-catalyzed reaction of vinyl bromide with dialkyl phosphite.

Mizoroki-Heck Reaction of Unstrained Aryl Ketones via Ligand-Promoted C-C Bond Olefination

Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is accomplished via palladium-catalyzed ligand-promoted C-C bond cleavage. Various (hetero)aryl ketones are compatible in the reaction, affording the alkene product in good to excellent yields. Further applications in the late-stage olefination of some drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By employing ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved via sequential ortho-C-H alkylation/ipso-Heck olefination.

Inverting External Asymmetric Induction via Selective Energy Transfer Catalysis: A Strategy to β-Chiral Phosphonate Antipodes

Enantiodivergent, catalytic reduction of activated alkenes relays stereochemical information encoded in the antipodal chiral catalysts to the pro-chiral substrate. Although powerful, the strategy remains vulnerable to costs and availability of sourcing bo

SAR of non-hydrolysable analogs of pyridoxal 5′-phosphate against low molecular weight protein tyrosine phosphatase isoforms

Kinases and phosphatases are key enzymes in cell signal transduction pathways. Imbalances in these enzymes have been linked to numerous disease states ranging from cancer to diabetes to autoimmune disorders. The two isoforms (IFA and IFB) of Low Molecular Weight Protein Tyrosine Phosphatase (LMW-PTP) appear to play a role in these diseases. Pyridoxal 5′-phosphate (PLP) has been shown to act as a potent but, impractical micromolar inhibitor for both isoforms. In this study, a series of non-hydrolysable phosphonate analogs of PLP were designed, synthesized and tested against the two isoforms of LMW-PTP. Assay results demonstrated that the best inhibitor for both isoforms was compound 5 with a Kis of 1.84 μM (IFA) and 15.6 μM (IFB). The most selective inhibitor was compound 16, with a selectivity of roughly 370-fold for IFA over IFB.

TEMPO and Silver-Mediated Intermolecular Phosphonylation of Alkenes: Stereoselective Synthesis of (E)-Alkenylphosphonates

An efficient method was developed towards the synthesis of alkenylphosphonates from simple olefins and phosphonate diesters. This method was enabled by the use of cheap and commercially available silver salts and TEMPO. This method exhibits of good functional group tolerance, specific (E)-selectivity for all olefins and vinyl selectivity for aliphatic olefins. A radical mechanism was proposed, and TEMPO was involved in the product formation step.

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.

Chemoselective Activation of Diethyl Phosphonates: Modular Synthesis of Biologically Relevant Phosphonylated Scaffolds

Phosphonates have garnered considerable attention for years owing to both their singular biological properties and their synthetic potential. State-of-the-art methods for the preparation of mixed phosphonates, phosphonamidates, phosphonothioates, and phos

Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates

A strategy for the direct functionalization strategy of inertial dialkyl phosphonates with hydroxy compounds to afford diverse mixed phosphonates with good yields and functional-group tolerance has been developed. Mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive PV species (phosphoryl pyridin-1-ium salt), a key intermediate for this new synthetic transformation, is generated in situ from dialkyl phosphonate in the presence of Tf2O/pyridine.