RESUMO
We report herein a reexamination of the reactions between sulfoxonium ylides and acetylenic esters. Continuing our previous study of conjugate additions using α-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 α-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 α-carbonyl vinyl sulfoxonium ylides in yields of up to 89%.
RESUMO
Imidoyl sulfoxonium ylides are presented for the first time as potential precursors to generate α-imino metal-carbene intermediates and applied in direct C-H functionalization reactions catalyzed by [Ir(cod)Cl]2 (4 mol %) to provide 2-substituted indoles (up to 70% yield) in just one step. This class of sulfur ylide is successfully obtained from imidoyl chloride and dimethylsulfoxonium methylide (23 new examples in 45-85% yield) or by imino group formation from the corresponding ß-keto sulfoxonium ylides and anilines in the presence of TiCl4 as a Lewis acid (9 examples in 33-94% yield).