While arguably arylmonophosphates are also accessible by alternative methods, the aryne phosphate reaction enables the straight-forward synthesis of otherwise difficult to access monoarylpyrophosphates. In fact, PPi proved to be a very efficient arynophile, leading to consistently high yields (scheme 2, B). To ensure turnover at lowered reaction temperature, the PPi equivalents had to be raised compared to the Pi case. Phenyldiphosphate 32, 3,4-dimethylphenyl-diphosphate 34 and pyrenyldiphosphate 36 were isolated in >90% yields. 2-Naphtyldiphosphate 33 was obtained in 62% yield and indolyldiphosphate 35 was accessed in 42% yield.