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

• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Thiago Barcellos,
• Claudio C. Silveira and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2021, 17, 234–244, doi:10.3762/bjoc.17.24

• 10.3762/bjoc.17.24 Abstract 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

• tautomers was possible, revealing them as significant intermediates for the mechanism elucidation. Keywords: α-alkylthio esters; α-alkylthio ketones; Bunte salts; C–C bond cleavage; β-keto esters; Introduction During the last ten years, sodium S-organyl sulfurothioates, also known as Bunte salts, were

• to α-sulfenylated amides (Scheme 1C) [52]. Inspired by those elegant pioneering studies, we explored the reaction of 1,3-dicarbonyl compounds with Bunte salts mediated by a base (Scheme 1D). The choice of NaOH as the base and its concentration were crucial to the selective synthesis of α-thio esters