3740-04-3Relevant articles and documents
Electron-transfer nucleophilic substitution reactions on neopentyl- and phenyl-substituted alkyl chlorides. Effect of the bridge length on the intramolecular electron-transfer catalysis
Duca Jr., Jose S.,Gallego, Mariana H.,Pierini, Adriana B.,Rossi, Roberto A.
, p. 2626 - 2629 (1999)
The nucleophilic substitution reaction of the chlorides RMe2CCH2Cl (R = Me, 4; Ph, 5a; PhCH2, 5b) and their relative reactivities toward diphenyl phosphide ions were studied under irradiation in liquid ammonia. The relative reactivities determined were k5a/k4 ? 9 and k5b/k4 ? 0.85. These reactions are proposed to occur through the SRN1 mechanism. The higher reactivity of 5a is explained on the basis of its higher electron affinity due to the phenyl substitution and the efficient intramolecular electron transfer from this group to the C-Cl σ* bond (intra-ET catalysis). Although 5b also has a phenyl ring, its lower reactivity is ascribed to a decrease in the rate of the intra-ET by elongation of the bridge in one methylene unit. The relative reactivity of 5a versus 5b (k5a/k5b, ? 6.4) is proposed to indicate the ratio of the intra-ET rates of the radical anions of both compounds. AMI calculations performed on the system are in agreement with the experimental results.
Room temperature, palladium-mediated P-arylation of secondary phosphine oxides
Bloomfield, Aaron J.,Herzon, Seth B.
supporting information, p. 4370 - 4373 (2012/10/29)
We show that a broad range of aryl iodides are efficiently coupled with secondary phosphine oxides using 1 mol % of a catalyst formed in situ from tris(dibenzylideneacetone)dipalladium and Xantphos (1). Scalemic (S)-methylphenylphosphine oxide [(S)-2e] is shown to undergo arylation without detectable stereoerosion. The application of this method to the synthesis of novel P-chiral phosphines and PCP ligands is demonstrated.
