Synthesis of Allyl Aryl Sulfone Derivatives from BaylisHillman Acetates in Water

Abstract

Various phenyl and p‐tolyl allyl sulfone derivatives were prepared stereoselectively by reacting BaylisHillman acetates with sodium 4‐R‐benzenesulfinate (R=H, Me) in H2O. The reaction was very efficient in providing the corresponding sulfone derivatives in good to excellent yields (Table).

Phosphine‐Catalyzed Diastereoselective [3 + 3] Annulation of Morita–Baylis–Hillman Carbonates with C,N‐Cyclic Azomethine Imines

“…We used the reaction of C , N ‐cyclic azomethine imine ( 1a ) with MBH carbonate ( 2a ) as the model reaction. In the absence of phosphine, the thermal [3 + 2] annulation of azomethine imine 1a with MBH carbonate 2a was not observed at room temperature, albeit an unexpected Ts addition product ( 4 ) was isolated in 28% yield (Table , entry 1) . In the presence of 20 mol% of Ph 3 P, no desired product was obtained, and only side product 4 was isolated (entry 2).…”

A Facile and Mild Synthesis of Trisubstituted Allylic Sulfones from Morita-Baylis-Hillman Carbonates

“…MBH carbonate 1 (0.1 mmol) and sodium sulfinate 2 (0.15 mmol) were mixed in MeCN (1 mL) and heated at 40 °C for 2 h. Then, the reaction mixture was concentrated under reduced pressure and the residue was diluted with toluene and purified by flash column chromatography on silica gel (petroleum ether/EtOAc) to afford the desired product 3a–o . Products 3a [33], 3d [26], 3f [26], 3k [26], 3l [27], 3n [33] and 3o [26] are known compounds.…”

“…The use of MBH adducts or their acetates as good starting materials for the trisubstituted allylic sulfones has been reported in some instances [26,27,28,29,30,31,32,33,34]. Although many sulfonyl precursors including sulfinate [26,27,28,29], p -toluenesulfonylmethylcyanide [30], arenesulfonyl cyanide [31], sulfinyl chloride [32], sulfonylhydrazide [33] and sulfinic acid [34] have been employed in this type of allylic sulfonylation, sulfinate is undoubtedly a cheap and easily available reagent. However, either a high reaction temperature [26,27] (70–80 °C, 6–16 h) or unconventional organic solvent (ionic liquids or polyethylene glycol) [28,29], accompanied with tedious work-up procedures, were required to ensure a high yield of the desired products.…”

“…Although many sulfonyl precursors including sulfinate [26,27,28,29], p -toluenesulfonylmethylcyanide [30], arenesulfonyl cyanide [31], sulfinyl chloride [32], sulfonylhydrazide [33] and sulfinic acid [34] have been employed in this type of allylic sulfonylation, sulfinate is undoubtedly a cheap and easily available reagent. However, either a high reaction temperature [26,27] (70–80 °C, 6–16 h) or unconventional organic solvent (ionic liquids or polyethylene glycol) [28,29], accompanied with tedious work-up procedures, were required to ensure a high yield of the desired products. Since MBH carbonates usually exhibit much superior reactivity to MBH acetates, we envisaged that they would be more susceptible to the nucleophilic attack by sulfinate.…”

Palladium-Catalyzed Stereoselective Formation of Substituted Allylic Thioethers and Sulfones

“…Such a manifold would thus offer a practical route toward the challenging stereoselective synthesis of tri- and even tetrasubstituted allylic thioethers and sulfones (upon oxidation) from simple and accessible precursors (Scheme , b). (Allylic) sulfone scaffolds are frequently observed in relevant pharmaceutical compounds, and thus, their synthesis is of significant importance …”