93-22-1Relevant academic research and scientific papers
C-F activation for C(sp2)-C(sp3) cross-coupling by a secondary phosphine oxide (SPO)-nickel complex
Müller, Valentin,Ghorai, Debasish,Capdevila, Lorena,Messinis, Antonis M.,Ribas, Xavi,Ackermann, Lutz
supporting information, p. 7034 - 7040 (2020/09/15)
A secondary phosphine oxide (SPO)-nickel catalyst allowed the activation of otherwise inert C-F bonds of unactivated arenes in terms of challenging couplings with primary and secondary alkyl Grignard reagents. The C-F activation is characterized by mild reaction conditions and high levels of branched selectivity. Electron-rich and electron-deficient arenes were suitable electrophiles for this transformation. In addition, this strategy also proved suitable to heterocycles and for the activation of C-O bonds under slightly modified conditions.
Terminal-Selective Functionalization of Alkyl Chains by Regioconvergent Cross-Coupling
Dupuy, Stéphanie,Zhang, Ke-Feng,Goutierre, Anne-Sophie,Baudoin, Olivier
, p. 14793 - 14797 (2016/11/23)
Hydrocarbons are still the most important precursors of functionalized organic molecules, which has stirred interest in the discovery of new C?H bond functionalization methods. We describe herein a new step-economical approach that enables C?C bonds to be constructed at the terminal position of linear alkanes. First, we show that secondary alkyl bromides can undergo in situ conversion into alkyl zinc bromides and regioconvergent Negishi coupling with aryl or alkenyl triflates. The use of a suitable phosphine ligand favoring Pd migration enabled the selective formation of the linear cross-coupling product. Subsequently, mixtures of secondary alkyl bromides were prepared from linear alkanes by standard bromination, and regioconvergent cross-coupling then provided access to the corresponding linear arylation product in only two steps.
Nickel-catalyzed alkylative cross-coupling of anisoles with grignard reagents via C-O bond activation
Tobisu, Mamoru,Takahira, Tsuyoshi,Morioka, Toshifumi,Chatani, Naoto
, 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.
