Switchable Divergent Synthesis of 3‐Dithiocarbamyl and 3‐Carbamothioyl Chromones Through Chromone Annulation Reactions of <i>o</i> ‐Hydroxyenaminones With CS ₂

A practical, highly atom‐economical and switchable α ‐C(sp 2 )−H (di)thiocarbamation/chromone annulation reaction for the divergent synthesis of two types of 3‐substituted chromones has been developed. A variety of 3‐dithiocarbamyl chromones and 3‐carbamothioyl chromones were constructed efficiently from readily available o ‐hydroxyphenylenaminones ( o ‐HPEs) and carbon disulfide (CS 2 ) via KIO 3 /DTBP cooperative catalytic oxidation. Notably, this transformation proceeds efficiently by recycling by‐product dimethylamine and employing equivalent amount of CS 2 . This strategy features high atom economy, mild reaction conditions, broad substrate scope, gram‐scale preparation and further derivatization.