2027-19-2Relevant articles and documents
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
, (2020)
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.
Nickel-catalyzed alkylative cross-coupling of anisoles with grignard reagents via C-O bond activation
Tobisu, Mamoru,Takahira, Tsuyoshi,Morioka, Toshifumi,Chatani, Naoto
supporting information, p. 6711 - 6714 (2016/06/14)
We report nickel-catalyzed cross-coupling of methoxyarenes with alkylmagnesium halides, in which a methoxy group is eliminated. A wide range of alkyl groups, including those bearing β-hydrogens, can be introduced directly at the ipso position of anisole derivatives. We demonstrate that the robustness of a methoxy group allows this alkylation protocol to be used to synthesize elaborate molecules by combining it with traditional cross-coupling reactions or oxidative transformation. The success of this method is dependent on the use of alkylmagnesium iodides, but not chlorides or bromides, which highlights the importance of the halide used in developing catalytic reactions using Grignard reagents.
Stereospecific nickel-catalyzed cross-coupling reactions of alkyl grignard reagents and identification of selective anti-breast-cancer agents
Yonova, Ivelina M.,Johnson, A. George,Osborne, Charlotte A.,Moore, Curtis E.,Morrissette, Naomi S.,Jarvo, Elizabeth R.
supporting information, p. 2422 - 2427 (2014/03/21)
Alkyl Grignard reagents that contain β-hydrogen atoms were used in a stereospecific nickel-catalyzed cross-coupling reaction to form C(sp 3)-C(sp3) bonds. Aryl Grignard reagents were also utilized to synthesize 1,1-diarylalkanes. Sev