Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates.

In pursuit of a more sustainable route to phosphorus-carbon (P-C) bond-containing chemicals, we herein report that phosphonates can be prepared by mechanochemical phosphorylation of acetylides using polyphosphates in a single step, redox-neutral process, bypassing white phosphorus (P 4 ) and other high-energy, environmentally hazardous intermediates. Using sodium triphosphate (Na 5 P 3 O 10 ) and acetylides, alkynyl phosphonates 1 can be isolated in yields of up to 32%, while reaction of sodium pyrophosphate (Na 4 P 2 O 7 ) and sodium carbide (Na 2 C 2 ) engendered, in an optimized yield of 63%, ethynyl phosphonate 2 , an easily isolable compound that can be readily converted to useful organophosphorus chemicals. Highly condensed phosphates like Graham's salt and bioproduced polyphosphate were also found to be compatible after reducing the chain length by grinding with orthophosphate. These results demonstrate the possibility of accessing organophosphorus chemicals directly from condensed phosphates and may offer an opportunity to move toward a "greener" phosphorus industry.