Selective synthesis of α-organylthio esters and α-organylthio ketones from β-keto esters and sodium S-organyl sulfurothioates under basic conditions

We described herein a selective method to prepare α-organylthio esters and α-organylthio ketones by the reaction of β-keto esters with sodium S-benzyl sulfurothioate or sodium S-alkyl sulfurothioate (Bunte salts) under basic conditions in toluene as the solvent at 100 °C. When 4 equivalents of a base were used, a series of differently substituted α-thio esters were obtained with up to 90% yield. On the other hand, employing 2 equivalents of a base, α-thio ketones were achieved after 18 h under air. Furthermore, after a shorter reaction time, the isolation of keto–enol tautomers was possible, revealing them as significant intermediates for the mechanism elucidation.

Iodine-catalyzed thioallylation of indoles using Bunte salts prepared from Baylis-Hillman bromides

A metal-free iodine-catalyzed regioselective thioallylation of indoles has been accomplished at room temperature by the Bunte salts prepared from Baylis-Hillman bromides. The resulting multi-functional C3 thioallylated indoles are achieved with...

Ag-Cu Copromoted Direct C2–H Bond Thiolation of Azoles with Bunte Salts as Sulfur Sources

A direct C2–H thiolation of azoles with Bunte salts was achieved under the combined action of copper and silver salts. This protocol could furnish various substituted 2-thioazoles in moderate to...

Synthesis of New Water-Soluble Bunte Salts Bearing Thieno[2,3-b]Pyridine-3-yl Substituents

Upon treatment with chloroacetyl chloride, 3-aminothieno[2,3-b]pyridines gave the corresponding chloroacetamides. The latter readily react with sodium thiosulphate to afford water soluble S-alkylthiosulphates with pharmacophoric heterocyclic units.

Transition metal-free α-Csp3–H oxidative sulfuration of benzyl thiosulfates with anilines to form N-aryl thioamides

A transition metal-free synthesis of N-aryl thioamides was realized by the oxidative sulfuration of Bunte salts in DMSO with anilines.