Hydrostannylation of Red Phosphorus: A Convenient Route to Monophosphines

The preparation of valuable and industrially relevant organophosphorus compounds currently depends on indirect multistep procedures involving difficult‐to‐handle white phosphorus as a common P atom source. Herein, we report a practical and versatile method for the synthesis of a variety of monophosphorus compounds directly from the bench‐stable allotrope red phosphorus (P(red)). The relatively inert P(red) was productively functionalised by using the cheap and readily available radical reagent tri‐n‐butyltin hydride, and subsequent treatment with electrophiles yields useful P(1) compounds. Remarkably, these transformations require only modest inert‐atmosphere techniques and use only reagents that are inexpensive and commercially available, making this a convenient and practical methodology accessible in most laboratory settings.