Metal-free and selective cleavage of unstrained carbon–carbon single bonds: Synthesis of β-ketosulfones from β-chlorohydrins and sodium sulfinates

<p>A metal-free protocol for the selective cleavage of unstrained C–C single bonds was developed. Under the catalysis of KI and in the presence of NaHCO<sub>3</sub>, the readily available <i>α</i>-chloro-β-hydroxy ketones underwent bond breaking and sulfonylation smoothly to afford β-ketosulfones with high efficiency and broad substrate scope. Mechanism investigations, both experimental and theoretical, showed that a retro-aldol cleavage/nucleophilic substitution sequence might be involved.</p>