Revisiting the Reaction of Sulfur Ylides with Acetylenic Esters: Synthesis of Trisubstituted 1,3-Dienes, α-Carbonyl Vinyl Sulfoxides and α-Carbonyl Vinyl Sulfoxonium Ylides

We report herein a reexamination of the reactions between sulfoxonium ylides and acetylenic esters. Continuing our previous study of conjugate additions using alpha-carbonyl sulfoxonium ylides, we came across an interesting transformation when dimethyl acetylenedicarboxylate (DMAD) was employed as a Michael acceptor. Trisubstituted electron-deficient 1,3-dienes and alpha-carbonyl vinyl sulfoxides were obtained for the first time from these sulfur ylides, in a stereoselective manner (exclusively forming the E-isomer), achieving yields of up to 70 % and 83 %, respectively. Selected dienes were subsequently utilized in the synthesis of novel nitrogen heterocycles. Interestingly, when di-tert-butyl acetylenedicarboxylate (DtBAD) or alkyl propiolates were evaluated, the isolated product arose from the classical Michael addition, yielding alpha-carbonyl vinyl sulfoxonium ylides in yields of up to 89 %.