6376-03-0Relevant academic research and scientific papers
LiI/TBHP Mediated Oxidative Cross-Coupling of P(O)–H Compounds with Phenols and Various Nucleophiles: Direct Access to the Synthesis of Organophosphates
Anitha, Thippani,Ashalu, Kashamalla Chinna,Sandeep, Mummadi,Mohd, Aabid,Wencel-Delord, Joanna,Colobert, Francoise,Reddy, Kallu Rajender
, p. 7463 - 7474 (2019/12/03)
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.
Transition State Analysis of the Reaction Catalyzed by the Phosphotriesterase from Sphingobium sp. TCM1
Bigley, Andrew N.,Xiang, Dao Feng,Narindoshvili, Tamari,Burgert, Charlie W.,Hengge, Alvan C.,Raushel, Frank M.
, p. 1246 - 1259 (2019/03/07)
Organophosphorus flame retardants are stable toxic compounds used in nearly all durable plastic products and are considered major emerging pollutants. The phosphotriesterase from Sphingobium sp. TCM1 (Sb-PTE) is one of the few enzymes known to be able to hydrolyze organophosphorus flame retardants such as triphenyl phosphate and tris(2-chloroethyl) phosphate. The effectiveness of Sb-PTE for the hydrolysis of these organophosphates appears to arise from its ability to hydrolyze unactivated alkyl and phenolic esters from the central phosphorus core. How Sb-PTE is able to catalyze the hydrolysis of the unactivated substituents is not known. To interrogate the catalytic hydrolysis mechanism of Sb-PTE, the pH dependence of the reaction and the effects of changing the solvent viscosity were determined. These experiments were complemented by measurement of the primary and secondary 18-oxygen isotope effects on substrate hydrolysis and a determination of the effects of changing the pKa of the leaving group on the magnitude of the rate constants for hydrolysis. Collectively, the results indicated that a single group must be ionized for nucleophilic attack and that a separate general acid is not involved in protonation of the leaving group. The Br?nsted analysis and the heavy atom kinetic isotope effects are consistent with an early associative transition state with subsequent proton transfers not being rate limiting. A novel binding mode of the substrate to the binuclear metal center and a catalytic mechanism are proposed to explain the unusual ability of Sb-PTE to hydrolyze unactivated esters from a wide range of organophosphate substrates.
