An iron-mediated vicinal difunctionalization of enamides and enecarbamates with sulfinic acid salts and alcohols is described. This reaction proceeds under mild conditions and furnishes the oxysulfonylated products in moderate to excellent yields. Moreover, the direct incorporation of sulfur dioxide into the sulfonylated products via organolithium chemistry has been achieved. The formed N-O-acetals are competent acylimine precursors. Their utilization as building blocks for the synthesis of biologically relevant β-amidosulfones is described as well.