Palladium(0)-Catalyzed Functionalization of Bromophosphinines

[PdL₂]-catalyzed (L = triphenyl- or trifurylphosphine) cross-coupling of 2,4,6-tribromo- or 2,6-dibro-mophosphinines with R-SnMe₃ derivatives yields the corresponding 2,6-di-R-phosphinines, where R = 2-furyl, 2-thienyl, 2-N-methylpyrrolyl, or C≡C—Ph. When R is 2-pyridyl, only the monosubstituted phosphinine is obtained. A similar cross-coupling reaction between 2,4,6-tribromo- or 2-bromophosphinines and (trimethylsilyl)diphenylphosphine gives either 2,6-bis(diphenylphosphino)- or 2-(diphenylphosphino)phosphinines according to the starting materials. In the case of 2,4,6-tribromophosphinines, the ortho selectivity of the functionalizations probably reflects an initial coordination of [PdL₂] to the phosphinine phosphorus.