343785-69-3Relevant academic research and scientific papers
A Cyclic Phosphate: Base and Metal Acetate Catalyzed Ring Opening
Wadsworth, William G.,Wadsworth, William S.
, p. 1631 - 1637 (1983)
Six-membered ring phosphates in which a good leaving group is absent undergo methanolysis to give acyclic products that can reclose to the original cyclic system.Under basic conditions the sequence is not stereospecific, which is explained by assuming an
SILICON-PHOSPHORUS ANALOGIES. NUCLEOPHILIC CATALYSIS IN THE ALCOHOLYSIS OF CHLOROPHOSPHORUS DERIVATIVES
Corriu, Robert J. P.,Lanneau, Gerard F.,Leclercq, Dominique
, p. 1959 - 1974 (2007/10/02)
The mechanism of the alcoholysis of chlorophosphonates and chlorophosphates in presence of nucleophilic catalysts like hexamethylphosphotriamide, pyridine and N-methylimidazole is discussed on the basis of kinetic and stereochemical results.We have proposed a mechanism for the reaction, which is governed by entropy, involving reaction of the alcohol with a pentacoordinated intermediate.This accounts for the differences in the stereochemical outcome and the rate equation which can be derived for the reaction with a variety of substrates in addition to the absence of common ion + solvent effects observed.
NUCLEOPHILIC SUBSTITUTIONS AT SILICON AND PHOSPHORUS. A COMPARISON OF CONTROLLING FACTORS
Corriu, R.J.P.
, p. 1 - 12 (2007/10/02)
The stereochemical behavior of functional organosilanes is explained considering electronic factors.The reactivity depends on the stereochemistry.Retention and /or inversion are controlled by a frontier orbital process.The same conclusions can be extended to the mechanism of nucleophilic substitution of halogenophosphorus compounds.The kinetic data show that the electronic interaction between the incoming nucleophile and the leaving group is very deep when they are both in the apical position of a tbp intermediate.By contrast, the influence of the nucleophile is minimized when the approach of the nucleophile affords a 90 deg angle, i. e. overall retention at phosphorus.The hydrolysis of silicates should be certainly more connected to the process of hydrolysis of phosphates through a mechanism involving pseudorotation of the pentacoordinated intermediates.
Fluoride Activation of Nucleophilic Displacement at Tetrahedral Phosphorus
Corriu, Robert J. P.,Dutheil, Jean-Pierre,Lanneau, Gerard F.
, p. 101 - 103 (2007/10/02)
Participation of fluoride anion in nucleophilic substitution at tetrahedral phosphorus implies the transient formation of trans-difluorophosphorane oxide.
