Stereochemistry and Product Distribution in the Thiono-Thiolo Rearrangement of Phosphorothioic Esters. 4. Role of Leaving-Group Solvation

Article abstract of DOI:10.1021/jo00321a019

The thiono-thiolo rearrangement of 1-3 in different protic acids was studied.On the basis of the product distribution and stereochemistry of the resulting phosphorothiolates, an ion-pair mechanism is postulated.Depending on the acidity of the reaction medium and the substrate concentration, internal ion-pair recombination and/or attack of the unprotonated substrate molecule on the dissociated ion pair have been taken into consideration in this postulate.