7735-87-7Relevant academic research and scientific papers
Experimental Tests of the Stereoelectronic Effect at Phosphorus: Nucleophilic Reactivity of Phosphite Esters
Taira, Kazunari,Mock, William L.,Gorenstein, David G.
, p. 7831 - 7835 (2007/10/02)
Triethyl phosphite rapidly reacts with ethyl benzenesulfenate or diethyl peroxide to yield pentaethoxyphosphorane.In contrast, 1-methyl-4-phospha-3,5,8-trioxabicyclooctane (1) fails to react with either electrophile to yield the expected bicyclic phosphorane 5.The poor reactivity of the bicyclic phosphite 1 is due to a kinetic rather than a thermodynamic barrier because 5 is formed smoothly from an equimolar mixture of P(OEt)5 and the triol 1,1,1-tris(hydroxymethyl)ethane.This result is interpreted in terms of the stereoelectronic effect.The order of nucleophilic reactivity of trialkyl phosphites with 3-benzylidene-2,4-pentanedione is also shown to be consistent with the stereoelectronic effect.The bicyclic phosphite 1 reacted 750 times slower than the pseudoequatorial 2-methoxy ester of hexahydrobenzo-1,3,2-dioxaphosphorinane in a Michael addition reaction with 3-benzylidene-2,4-pentanedione.
The Reaction of 1-Substituted 3,4-Dimethyl-Δ3-phospholens with Diethyl Peroxide: a Correlation Between Rate and 31P Nuclear Magnetic Resonance Shift
Hammond, Philip J.,Scott, Graham,Hall, C. Dennis
, p. 205 - 210 (2007/10/02)
The reactions of a variety of 1-X-3,4-dimethyl-Δ3-phospholens (where X=Br, Me, Ph, NMe2, SEt, H, and OR) with diethyl peroxide are described.The rates of reaction show a broad correlation with the 31P n.m.r. chemical shifts of the starting phospholens, with low field shifts corresponding to the highest reactivity.The results are discussed in terms of the biphilic mechanism for the reaction of trico-ordinate phosphorus compounds with weak ?-bonds.
