One-pot synthesis of primary phosphines from white phosphorus

Aryl and alkyl chlorides are inexpensive and readily accessible, making them ideal reagents for converting white phosphorus (P₄) into primary phosphines RPH₂. However, methods for achieving this transformation directly, bypassing undesired intermediates like PCl₃, have remained elusive. This report describes the ‘one-pot’ synthesis of primary organophosphines from P₄ using organotin compounds, including a multi-gram synthesis of PhPH₂ featuring efficient recovery of organotin reagents for potential recycling.