A new synthesis of β,γ-unsaturated esters and allenic esters with construction of a carbon–carbon bond between α- and β-positions by the reaction of magnesium alkylidene carbenoids with lithium ester enolates

Abstract

Treatment of lithium ester enolates with magnesium alkylidene carbenoids, generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride via the sulfoxide–magnesium exchange reaction, gave β,γ-unsaturated esters in moderate to good yields. When this reaction was conducted with the lithium ester enolates of α-chlorocarboxylic acid esters, allenic esters were obtained. This procedure provides an unprecedented way for the synthesis of β,γ-unsaturated esters and allenic esters from ketones with the construction of a carbon–carbon bond between α- and β-positions.