4519-33-9Relevant academic research and scientific papers
The Tetraethylphosphorodiamidate (OP(O)(NEt2)2) Directed Metalation Group (DMG). Directed ortho and Lateral Metalation and the Phospha Anionic Fries Rearrangement
Alessi, Manlio,Patel, Jignesh J.,Zumbansen, Kristina,Snieckus, Victor
supporting information, p. 2147 - 2151 (2020/03/13)
We report on the tetraethylphosphorodiamidate (-OP(O)(NEt2)2) group as an effective directed metalation group (DMG). Lithiation-electrophile quench of 1 provides a general synthesis of ortho-substituted aryl and naphthyl phosphorodiamidates 4-8. We also describe the phospha anionic ortho-Fries (AoF) rearrangement of the phosphorodiamidates 1a,1ba2 or 3 and its vinylogous counterpart to the ortho-tolyl phosphorodiamidates 5ba 13. Intermolecular competition experiments demonstrate the approximately equal DMG strength of the-OP(O)(NEt2)2 and the most powerful OCONEt2 groups.
Tetraethylphosphorodiamidate-Directed Metalation Group: Directed Ortho and Remote Metalation, Cross Coupling, and Remote Phospha Anionic Fries Rearrangement Reactions
Alessi, Manlio,Blackburn, Thomas,Patel, Jignesh J.,Sawinski, Hannah,Snieckus, Victor
supporting information, (2020/05/18)
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.
