These optimized reaction conditions were applied in a first cluster of transformations: arynes derived from o-silylaryltriflates were reacted with Pi (17) and PPi (18) leading to (pyro-)phosphomonoesters (26, scheme 2, A). An excess of Pi and PPi was applied in these transformations. In the case of Pi, 60 °C led to the highest yields, but PPi reactions required room temperature to avoid anhydride hydrolysis and over-arylation. The products (scheme 2, B) were purified chromatographically and usually isolated as TBA or TEA salts. Following this procedure, phenylphosphate 27 was synthesized in 88% yield. 2-Naphtylphosphate 28 was accessed from the corresponding naphtyne precursor in 65% yield and 3,4dimethylphenylphosphate (29) was isolated in a yield of 92%. Garg's indole 4,5-indolyne-precursor was transformed to indolylphosphate 30 in 41% yield, in a regioisomeric ratio of 96:4 (5-30:4-30). The observed regioisomeric preference towards C5-30 is in accordance with literature precedence and can be explained by Garg's aryne distortion model. Furthermore, we developed a new pyrene-derived aryneprecursor (SI-19) that was transformed successfully into the corresponding pyrenyl-phosphate 31 in 71% yield. The pyren-2yl regioisomer was preferentially formed in a ratio of 62:38. Presumably steric effects as well as aryne distortion synergistically direct the phosphate to pyrene's C2 position, further supported by an increase in selectivity for the bulkier PPi. We envision the reaction mechanism as a proton-coupled nucleophilic addition of phosphates (scheme 2, C) to arynes. Inter-and intramolecular proton transfer both seem plausible, as both water content in TBAF solutions and residual phosphate protons from the TBA salt, are suitable H + -sources. Consistently, the application of MeCN-d3 as solvent did not lead to deuterium incorporation into the product (scheme 2C).