Copper-Catalyzed Phosphorothiolation/Seleno(Telluro)phosphorylation of Vinylsulfonium Salts with P(III)-nucleophiles via the Insertion of Elemental Sulfur/Selenium/Tellurium

Abstract

A novel and facile copper-catalyzed phosphorothiolation and seleno(telluro)phosphorylation of vinylsulfonium salts with P(III)-nucleophiles for constructing C-Z-P(V) bonds (Z = S, Se, Te) by activating selenium, tellurium and sulfur powder in-situ has been established. The phosphorylation process in this system may involve the Michaelis-Arbuzov rearrangement as the initial step. Vinylsulfonium salts with various substituents and different types of P(III)-nucleophiles demonstrated excellent substrate suitability, resulting in the synthesis of the expected products with moderate to good yields. The model reaction is readily scalable to gram-level experiments under optimized conditions. Additionally, a possible mechanism for this transformation was proposed based on insights gained from stepwise control experiments and 31P NMR tracking experiments. To the best of our knowledge, this is the first method to activate inorganic tellurium in-situ using a phosphorylation source to form P-Te bonds directly. The P-Te compounds synthesized via this method exhibit superior activity against methicillin-resistant Staphylococcus aureus (MRSA).