Direct Synthesis of Benzo[]fluorenyl Thiophosphates via Tandem Cyclization of Diynols with (RO)P(O)SH.

A general and metal-free protocol for the construction of benzo[]fluorenyl thiophosphates was developed through the cascade cyclization of easily prepared diynols and (RO)P(O)SH, with water as the only byproduct. The novel transformation involved the allenyl thiophosphate as the key intermediate, followed by Schmittel-type cyclization to achieve the desired products. Notably, (RO)P(O)SH acted not only as a nucleophile but also as an acid-promoter to initiate the reaction.