36912-31-9Relevant academic research and scientific papers
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.
Silicon Phosphorus Analogies. Fluoride Activation of Nucleophilic Displacement at the Tetrahedral Phosphorus: An Example of Nucleophilic Assistance to Nucleophilic Substitution. 3
Corriu, Robert J. P.,Dutheil, Jean-Pierre,Lanneau, Gerard F.
, p. 1060 - 1065 (2007/10/02)
We report a mechanistic study of the activation of alcoholysis of the P-X bond (X= Cl, F) by F(1-).Cis and trans isomers of 2-halogeno-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinanes, 1 and 2, or their 2-thio analogues, 3 and 4, and epimeric 2-h
A Cyclic Phosphate: Base and Metal Acetate Catalyzed Ring Opening
Wadsworth, William G.,Wadsworth, William S.
, p. 1631 - 1637 (2007/10/02)
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
Analogies between silicon and phosphorus stereochemistry-II. Influence of the attacking anion upon the stereochemistry of nucleophilic displacement at tetrahedral phosphorus
Corriu,Dutheil,Lanneau
, p. 3681 - 3687 (2007/10/02)
The stereochemistry of reactions of cyclic halogenophosphates with a representative series of p-substituted aryloxides emphasizes the relative influence of the attacking anion. For a given leaving group, the stereochemistry depends essentially upon the electronic character of the p-substituent and the ion-pair dissociation of the nucleophile. Both stereochemical and kinetic data rule out a cation-assisted mechanism to explain retention at phosphorus. Meanwhile, a comparison between SN2(P) and SN2(Si) suggests similar mechanisms in the two series. Retention and/or inversion are the consequence of two competing reactions of similar energies. The stereochemistry is determined by the factors which affect the approach of the nucleophile to give two initial intermediates of different geometries.
