Sustainable phos-phorus functionali-zation with disulfides

White phosphorus (P4) is the common starting point from which almost all commercially relevant monophosphorus compounds are prepared. Most current industrial synthesis routes rely on multiple reaction steps and/or extremely hazardous reagents, intermediates or waste. When developing new phosphorus functionalization routes, sustainability, simplicity, high yields and cost-effectiveness are all fundamental, ideally in the sense of a circular economy approach. Catalysis is a cornerstone in green approaches.

Direct transformation of both white and red phosphorus into valuable monophosphorus products is done via initial oxidation by aryl disulfides followed by quenching with nucleophiles. The inventive process provides access routes to diverse P-C, P-N and P-O bonded products in good yields using inexpensive and easy-to-handle reagents. By isolating the thiolate by-products 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.