349-97-3Relevant articles and documents
Highly Site-Selective Formation of Perfluoroalkylated Anilids via a Protecting Strategy by Molybdenum Hexacarbonyl Catalyst
Yuan, Chunchen,Dai, Ping,Bao, Xiaoguang,Zhao, Yingsheng
, p. 6481 - 6484 (2019)
Introducing a perfluoroalkyl group on the aromatic ring with high site selectivity remains a challenging area in organofluorine chemistry. We herein report a highly para-selective C-H perfluoroalkylation of aniline substrates using the molybdenum hexacarbonyl catalyst. Various substituted anilids derived from anilids were well-tolerated, affording the corresponding products in moderate to good yields. Preliminary mechanism studies and density functional theory calculations revealed the coordination of Mo catalyst with amides as the key factor to realize para selectivity.
Acetonitrile and benzonitrile as versatile amino sources in copper-catalyzed mild electrochemical C-H amidation reactions
Budnikova, Yulia,Kononov, Alexander,Rizvanov, Ildar,Strekalova, Sofia
, p. 37540 - 37543 (2021/12/07)
A mild, efficient electrochemical approach to the site-selective direct C-H amidation of benzene and its derivatives with acetonitrile and benzonitrile has been developed. It has been shown that joint electrochemical oxidation of various arenes in the presence of a copper salt as a catalyst and nitriles leads to the formation of N-phenylacetamide from benzene and N-benzylacetamides from benzyl derivatives (up to 78% yield). A favorable feature of the process is mild conditions (room temperature, ambient pressure, no strong oxidants) that meet the criteria of green chemistry.
Mechanistic Insight into Copper-Mediated Trifluoromethylation of Aryl Halides: The Role of CuI
Jin, Yuxuan,Leng, Xuebing,Liu, He,Shen, Qilong,Wu, Jian
supporting information, p. 14367 - 14378 (2021/09/13)
The synthesis, characterization, and reactivity of key intermediates [Cu(CF3)(X)]-Q+ (X = CF3 or I, Q = PPh4) in copper-mediated trifluoromethylation of aryl halides were studied. Qualitative and quantitative studies showed [Cu(CF3)2]-Q+ and [Cu(CF3)(I)]-Q+ were not highly reactive. Instead, a much more reactive species, ligandless [CuCF3] or DMF-ligated species [(DMF)CuCF3], was generated in the presence of excess CuI. On the basis of these results, a general mechanistic map for CuI-promoted trifluoromethylation of aryl halides was proposed. Furthermore, on the basis of this mechanistic understanding, a HOAc-promoted protocol for trifluoromethylation of aryl halides with [Ph4P]+[Cu(CF3)2]- was developed.
