Visible-Light-Driven Z-Selective Reaction of Methyl Ketones with DMSO: A Mild Synthetic Approach to Methylthio-Substituted 1,4-Enedione Promoted by Selectfluor™

Here we disclose a simple, visible-light-driven Z-selective synthesis of methylthio-substituted 1,4-enedione in a single step promoted by Selectfluor. Dimethyl sulfoxide is used as both the ‘thio’ source and the solvent. Molecular iodine and potassium persulfate are used as catalyst and oxidant, respectively. White light (CFL-30W) is used as the light source. The proposed mechanism involves a Kornblum reaction followed by aldol reaction.

PHENOXATHIIN CHEMISTRY. NEW CARBONYL COMPOUNDS AND DERIVATIVES

Starting with 2-acetylphenoxathiin , 2-ω-bromoacetylphenoxathiinyl-10, 10-dioxide 2 was obtained. By means of the Kornblum reaction the corresponding glyoxal 4 was synthesized. From compound 2, the aminothiazole 3 and the 1,4-diketone 7 were also obtained. By the reaction of 2-ω-bromoacetylphenoxathiin 8 and sodium acetylacetonate "one-pot" synthesis of 1,4-diketone 9 was performed. Compound 9 was converted to pyrrolophenoxathiin 11 and 1,4-diketone 7. Starting with the brominated derivative 8 the aminoketones 12 and 13 were obtained. The new compounds were characterized by spectral methods CH-and 13C-NMR, IR, MS).

PHENOXATHIIN CHEMISTRY SYNTHESIS BASED ON 2-ω-BROMOACETYLPHENOXATHIIN

Starting from 2-ω-bromoacetylphenoxathiin and using the Kornblum reaction, the corresponding glyoxal 2 was synthesized. This was used for the syntheses of the monoxime 3, dioxime 4, and quinoxalinyl 5 derivatives. By treatment with thiourea 4-(2-phenoxathiinyl)-2-aminothiazole hydrobromide 7 was obtained. Some new ammonium and phosphonium salts were also prepared. Chemical and spectral data supporting the structure of the newly synthesized compounds are also presented.