Metal‐Free Selective C−S Bond Cleavage of Thioethers to Access β‐Alkoxy Carbonyl Compounds.

A metal‐free C(sp3)−S bond cleavage of β‐alkylthio carbonyl compounds in the presence of Selectfluor is described. This novel strategy realizes the C−S bond cleavage and subsequent C−O bond formation, providing a facile and efficient method to construct different important β‐alkoxy carbonyl compounds with moderate to good yields and good functional groups tolerance. Moreover, our mechanistic studies also prove that two different mechanisms including the oxidant and thionium ion intermediate pathway may exist in this process. [ABSTRACT FROM AUTHOR]