Design, Synthesis, and Applications of ortho-Sulfur Substituted Arylphosphanes

Ortho-sulfur substituted arylphosphine oxides and arylphosphonates are the precursors of orthosulfurated arylphosphanes, which are widely utilized as ligands in transition metal-catalyzed reactions. However, efficient synthetic methods to access such compounds are sparse. Herein, highly valuable ortho-sulfur substituted arylphosphine oxides and arylphosphonates were constructed via difunctionalization of aryne precursors with P(O)H and elemental sulfur. This method avoids the use of transition metal catalysts and corrosive phosphorus chloride. The synthetic utility of this reaction is further demonstrated by the reduction of the synthesized products to access monophosphine ligands and their applications in cross-coupling reactions. Moreover, by introducing an alkyne moiety into the P(O)H substrate, cyclic sulfur-containing phosphines could be obtained in a one-pot reaction, which represents a new P,S structure that is inaccessible by known strategies. [GRAPHICS] .