4783-78-2Relevant articles and documents
Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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Paragraph 0134-0138; 0140, (2021/05/29)
The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
Mechanochemical Solvent-Free Catalytic C?H Methylation
Ni, Shengjun,Hribersek, Matic,Baddigam, Swarna K.,Ingner, Fredric J. L.,Orthaber, Andreas,Gates, Paul J.,Pilarski, Lukasz T.
supporting information, p. 6660 - 6666 (2020/12/18)
The mechanochemical, solvent-free, highly regioselective, rhodium-catalyzed C?H methylation of (hetero)arenes is reported. The reaction shows excellent functional-group compatibility and is demonstrated to work for the late-stage C?H methylation of biologically active compounds. The method requires no external heating and benefits from considerably shorter reaction times than previous solution-based C?H methylation protocols. Additionally, the mechanochemical approach is shown to enable the efficient synthesis of organometallic complexes that are difficult to generate conventionally.
Benzylic C?H Functionalisation by [Et3SiH+KOtBu] leads to Radical Rearrangements in o-tolyl Aryl Ethers, Amines and Sulfides
Arokianathar, Jude N.,Kolodziejczak, Krystian,Bugden, Frances E.,Clark, Kenneth F.,Tuttle, Tell,Murphy, John A.
supporting information, p. 2260 - 2267 (2020/05/06)
Reaction of Et3SiH+KOtBu with diaryl ethers, sulfides and amines that feature an ortho alkyl group leads to rearrangement products. The rearrangements arise from formation of benzyl radicals, likely formed through hydrogen atom abstraction by triethylsilyl radicals. The rearrangements involve cyclisation of the benzyl radical onto the partner arene, which, from computation, is the rate determining step. In the case of diaryl ethers, Truce-Smiles rearrangements arise from radical cyclisations to form 5-membered rings, but for diarylamines, cyclisations to form dihydroacridines are observed. (Figure presented.).
