Metal‐Free Visible‐Light‐Induced Direct Synthesis of Alkyl‐Substituted Phosphonodithioates from White Phosphorus (P₄)

Abstract The direct synthesis of organic phosphorus compounds from white phosphorus (P 4 ) is a longstanding challenge in organic synthesis. Here, we present a novel visible light‐induced three‐component functionalization reaction that integrates P 4 , disulfide compounds, and N ‐hydroxyphthalimide (NHPI) esters to produce alkyl‐substituted phosphonodithioates in a one‐pot process. Using 2,4,5,6‐tetrakis(carbazol‐9‐yl)‐1,3‐dicyanobenzene (4CzIPN) as a photocatalyst, blue LEDs (456 nm) as the light source, and N , N ‐diisopropylethylamine (DIPEA) as the reducing agent in an acetone‐toluene solvent system, this method achieves moderate to good yields of structurally diverse phosphonodithioates. The reaction proceeds under mild conditions, ensures complete conversion of P 4 , avoids chlorination, and uses inexpensive, readily available starting materials, offering potential for large‐scale applications.