Ph₃PCN₂: A stable reagent for carbon-atom transfer

Precise modification of a chemical site in a molecule at the single-atom level is one of the most elegant yet difficult transformations in chemistry. A reagent specifically designed for chemoselective introduction of monoatomic carbon is a particularly formidable challenge. Here, we report a straightforward, azide-free synthesis of a crystalline and isolable diazophosphorus ylide, Ph₃PCN₂, a stable compound with a carbon atom bonded to two chemically labile groups, triphenylphosphine (PPh₃) and dinitrogen (N₂). Without any additives, the diazophosphorus ylide serves as a highly selective transfer reagent for fragments, including Ph₃PC, to deliver phosphorus ylide-terminated heterocumulenes and CN₂ to produce multisubstituted pyrazoles. Ultimately, even exclusive carbon-atom transfer is possible. In reactions with aldehydes and acyclic and cyclic ketones (R₂C=O), the carbon-atom substitution forms a vinylidene (R₂C=C:) en route to alkynes or butatrienes.