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.
Dehydrative Beckmann rearrangement and the following cascade reactions
Liu, Yinghui,Wei, Yongjiao,Xie, Lan-Gui
supporting information, (2021/11/16)
The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam. By strategically using the in situ generated Appel's salt or Mitsunobu's zwitterionic adduct as the dehydrating agent, a series of Beckmann rearrangement and following cascade reactions have been developed herein. The protocol allows the conversion of various ketoximes into amide, thioamide, tetrazole and imide products in modular procedures. The generality and tolerance of functionalities of this method have been demonstrated.
Cu(OTf)2-Mediated Cross-Coupling of Nitriles and N-Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**
Bell, Nicola L.,Xu, Chao,Fyfe, James W. B.,Vantourout, Julien C.,Brals, Jeremy,Chabbra, Sonia,Bode, Bela E.,Cordes, David B.,Slawin, Alexandra M. Z.,McGuire, Thomas M.,Watson, Allan J. B.
supporting information, p. 7935 - 7940 (2021/03/03)
Metal-catalyzed C–N cross-coupling generally forms C?N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C–N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.
