Reaction of Lithium Enolates with Carbon Disulfide: Synthesis of O-(1-Alkoxy-2,2-dialkylvinyl) S-Alkyl Dithiocarbonates

Article abstract of DOI:10.1021/jo00284a039

The reaction of lithium enolates 5, generated from esters 4 having only one α-hydrogen atom, with carbon disulfide at -78 deg C followed by alkylation with alkyl halide afforded O-(1-alkoxy-2,2-dialkylvinyl) S-alkyl dithiocarbonates (7) in excellent yields (84-95percent).An unambiguous structural assignment was made with the help of spectral and microanalytical data.A plausible mechanism has been proposed, in light of available literature, that explains the results of the reaction of enolates with carbon disulfide.The transformation is significant from both the synthetic and mechanistic points of view.These products have not previously been reported, and compound 8 was reported to be the primary product of the reaction of lithium enolate with carbon disulfide.This report represents the first example of formation of a C-O bond between the oxygen of an enolate and the carbon disulfide.