Stereochemical properties of 1,3-bissulfonium salts and 1,3-bissulfonium ylides

Abstract

Ten acyclic and two cyclic 1,3-bissulfonium bistetrafluoroborates have been synthesized by appropriate modification of the literature procedures for the preparation of such compounds. The acyclic salts are deprotonated readily by one molar-equivalent of potassium hydroxide to give 1,3-bissulfonium ylides. However, under the same conditions, the cyclic salts decompose. Hydrogen exchange experiments reveal that the C2 hydrogens of the cyclic salts are significantly less acidic than the C2 hydrogens of the acyclic salts. The relative acidities of the C2 hydrogens of the cyclic salts depend upon the medium and upon the configuration and conformation of the molecule, and preliminary attempts have been made to associate the kinetic and thermodynamic acidities of these hydrogens with their specific stereochemical environments.Deprotonation of a 1,3-bissulfonium salt is accompanied by a decrease of at least 5 kcal/mol in the barrier to pyramidal inversion at sulfur. However, attempts to establish the static and dynamic behaviour at the carbanionic centre were not successful.