Addition of Grignard and organolithium reagents to the negatively charged sulfur atom of 2,2-bis(diethylamino)ethan-2-ylium-1-dithioate

Article abstract of DOI:10.1246/cl.1998.321

A range of Grignard and organolithium reagents added to the negatively charged sulfur atom of the inner salt 1, despite the presence of the positively charged carbenium carbon, to give enethiolates 4, which were methylated by MeI to give dithioacetals 3 as the final product in excellent yields. A mechanism involving a single-electron-transfer process from nucleophiles to 1 is presented for this thiophilic addition.