Closing the Loop: Low‐Waste Phosphorus Functionalization Enabled by Simple Disulfides

Abstract Useful monophosphorus products are obtained from both white and red phosphorus via a simple strategy involving initial oxidation by aryl disulfides followed by quenching with nucleophiles. Direct transformations of elemental phosphorus are usually very challenging, forcing chemists to instead rely on inefficient and hazardous multi‐step methods. However, here they are achieved using inexpensive and easy‐to‐handle reagents, providing access to diverse P−C, P−N and P−O bonded products in good yields. By isolating the thiolate byproducts of these reactions, a simple, closed loop can be achieved that produces only minimal, benign waste byproducts, in contrast to other direct methods. This closed loop can even be elaborated into a true (electro)catalytic cycle, which is extremely rare in the field of elemental phosphorus functionalization.