2027-19-2Relevant academic research and scientific papers
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.
Ni-catalyzed reductive decyanation of nitriles with ethanol as the reductant
Wu, Ke,Ling, Yichen,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Jin, Liqun,Hu, Xinquan
supporting information, p. 2273 - 2276 (2021/03/09)
A nickel-catalyzed reductive decyanation of aromatic nitriles has been developed, in which the readily available and abundant ethanol was applied as the hydride donor. Various functional groups on the aromatic rings, such as alkoxyl, amino, imino and amide, were compatible in this catalytic protocol. Heteroaryl, benzylic and alkenyl nitriles were also tolerated. Mechanistic investigation indicated that ethanol provided hydride efficientlyviaβ-hydride elimination in this reductive decyanation.
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.
Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C-O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination
Liu, Xiangqian,Hsiao, Chien-Chi,Kalvet, Indrek,Leiendecker, Matthias,Guo, Lin,Schoenebeck, Franziska,Rueping, Magnus
supporting information, p. 6093 - 6098 (2016/05/19)
In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.
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
Functional-group-tolerant, nickel-catalyzed cross-coupling reaction for enantioselective construction of tertiary methyl-bearing stereocenters
Wisniewska, Hanna M.,Swift, Elizabeth C.,Jarvo, Elizabeth R.
supporting information, p. 9083 - 9090 (2013/07/26)
The first Negishi nickel-catalyzed stereospecific cross-coupling reaction of secondary benzylic esters is reported. A series of traceless directing groups is evaluated for ability to promote cross-coupling with dimethylzinc. Esters with a chelating thioether derived from commercially available 2-(methylthio)acetic acid are most effective. The products are formed in high yield and with excellent stereospecificity. A variety of functional groups are tolerated in the reaction including alkenes, alkynes, esters, amines, imides, and O-, S-, and N-heterocycles. The utility of this transformation is highlighted in the enantioselective synthesis of a retinoic acid receptor agonist and a fatty acid amide hydrolase inhibitor.
Nanoporous gold-catalyzed [4+2] benzannulation between ortho- alkynylbenzaldehydes and alkynes
Asao, Naoki,Menggenbateer,Seya, Yohei,Yamamoto, Yoshinori,Chen, Mingwei,Zhang, Wei,Inoue, Akihisa
supporting information; experimental part, p. 66 - 69 (2012/03/08)
Nanoporous gold material exhibits a catalytic activity on the benzannulation reaction between ortho-alkynylbenzaldehydes and alkynes. The catalyst is easily recoverable and can be reused several times without leaching and loss of activity. Georg Thieme Verlag Stuttgart. New York.
