1453101-19-3Relevant academic research and scientific papers
TRANSITION METAL-CATALYZED IMIDATION OF ARENES
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Paragraph 00248; 00249, (2015/03/13)
The present invention provides novel transition metal complexes (e.g., complexes of any one of Formulae (C1) to (C25)) that include an amine-N-oxide motif. The invention also provides methods of using these transition metal complexes in preparing N-aryl or N- heteroaryl sulfonimides (e.g., compounds of Formula (I)) and aryl or heteroaryl amines (e.g., compounds of Formula (II)). The inventive methods involve imidation of arenes and heteroarenes (e.g., compounds of Formula (A)) using an imidating agent (e.g., a compound of Formula (B), such as N-fluorobenzenesulfonimide (NFBS or NFSI)) in the presence of a single-electron reductant (e.g., an Ag(I) or Ru(II) salt).
Pd-catalyzed aryl C-H imidation with arene as the limiting reagent
Boursalian, Gregory B.,Ngai, Ming-Yu,Hojczyk, Katarzyna N.,Ritter, Tobias
supporting information, p. 13278 - 13281 (2013/09/24)
An amine-N-oxide-ligated palladium complex, in conjunction with a silver cocatalyst, catalyzes imidation of arenes by the reagent N- fluorobenzenesulfonimide. The reaction enables imidation of a variety of arenes at or below room temperature, requires no coordinating directing group on the substrate, and gives synthetically useful yields with only 1 equiv of arene. Mechanistic data implicate an unusual mechanism devoid of commonly invoked organometallic intermediates: oxidation of the Pd catalyst occurs as the turnover-limiting step, while C-H bond functionalization occurs subsequently at a high oxidation state of the catalyst.
