TY - JOUR A1 - Kazmierczak, Jean C. A1 - Cargnelutti, Roberta A1 - Barcellos, Thiago A1 - Silveira, Claudio C. A1 - Schumacher, Ricardo F. T1 - Selective synthesis of α-organylthio esters and α-organylthio ketones from β-keto esters and sodium S-organyl sulfurothioates under basic conditions JF - Beilstein Journal of Organic Chemistry PY - 2021/// VL - 17 SP - 234 EP - 244 SN - 1860-5397 DO - 10.3762/bjoc.17.24 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.17.24 KW - α-alkylthio esters KW - α-alkylthio ketones KW - Bunte salts KW - C–C bond cleavage KW - β-keto esters N2 - 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. ER -