Tetraethylphosphorodiamidate-Directed Metalation Group: Directed Ortho and Remote Metalation, Cross Coupling, and Remote Phospha Anionic Fries Rearrangement Reactions.

The linked directed ortho and remote metalation (DoM and DreM) and cross-coupling reactions of aryl phosphorodiamidates (Ar-OP(O)(NEt2)2) is reported. The o-iodo and o-boronato aryl tetraethylphosphorodiamidates 3, prepared by DoM, undergo orthogonal Ni- and Pd-catalyzed Suzuki-Miyaura cross coupling to furnish biaryls 4 and 5 in good to excellent yields. Silicon group protection of biaryl 4 via DoM followed by previously unobserved DreM phospha anionic Fries rearrangement affords biaryls 11 which, under acidic conditions, furnish oxaphosphorine oxides 12.