Convenient Access to Arylated Spirocyclic Bisphosphonates

The synthesis of P‐arylated spirocyclic bisphosphonates is described. The title compounds were generated through a process that combined transesterification with a palladium catalyzed P‐arylation. The cross‐coupling step could be carried out at room temperature using aryl iodides, while analogous reactions involving aryl bromides required heating. Nitrogen, oxygen, and sulfur containing heterocycles were also successfully incorporated into the framework. Using this approach 20 new arylated compounds were generated bearing a range of electrophiles and functional groups. For the more reactive aryl iodides, the catalyst loading could be decreased to 0.3 % Pd per P−H group in scaled‐up versions of the method. The two‐step process does not require the use of chlorophosphorus reagents.