861796-02-3Relevant academic research and scientific papers
Transition metal-free N-arylation of secondary amides through iodonium salts as aryne precursors
Wang, Ming,Huang, Zhijian
supporting information, p. 10185 - 10188 (2016/11/11)
By using a diaryliodonium salt as a benzyne precursor, a transition metal-free approach for N-arylation of secondary amides is developed. This novel benzyne precursor, which can be prepared easily by a one step process from an aryl iodide, shows different reactivities with previous benzyne precursors in the N-arylation reaction. Mechanistic studies confirm the involvement of benzyne species (generated in situ from the diaryliodonium salts) as key intermediates.
Pd-catalyzed N-arylation of secondary acyclic amides: Catalyst development, scope, and computational study
Hicks, Jacqueline D.,Hyde, Alan M.,Cuezva, Alberto Martinez,Buchwald, Stephen L.
supporting information; experimental part, p. 16720 - 16734 (2010/04/04)
We report the efficient N-arylation of acyclic secondary amides and related nucleophiles with aryl nonaflates, triflates, and chlorides. This method allows for easy variation of the aromatic component in tertiary aryl amides. A new biaryl phosphine with P-bound 3,5-(bis)trifluoromethylphenyl groups was found to be uniquely effective for this amidation. The critical aspects of the ligand were explored through synthetic, mechanistic, and computational studies. Systematic variation of the ligand revealed the importance of (1) a methoxy group on the aromatic carbon of the "top ring" ortho to the phosphorus and (2) two highly electron-withdrawing P-bound 3,5-(bis)trifluoromethylphenyl groups. Computational studies suggest the electron-deficient nature of the ligand is important in facilitating amide binding to the LPd(II)(Ph)(X) intermediate.
