Rh(III)‐Catalyzed Direct Amination of Aromatic Ketoximes Enabled by Potassium Acetate

Abstract

A method to achieve rhodium(III)‐catalyzed, potassium acetate enabled intermolecular C–H amination of ketoximes using various benzenesulfonamide, especially 4‐nitrobenzenesulfonamide is reported. Various aryl ketoximes substituted with electron‐withdrawing functional groups were all well tolerated and produced the corresponding products in moderate to good yields. A preliminary mechanistic study revealed that potassium acetate is essential to realizing intermolecular amination.

Copper-Catalyzed Intramolecular Olefinic C(sp2)–H Amidation for the Synthesis of γ-Alkylidene-γ-lactams

“…Cross-dehydrogenative coupling (CDC) of C(sp 2 )–H/N–H bonds is one of the most straightforward methods for forming C(sp 2 )–N bonds [ 1 , 2 , 3 , 4 ], which are found in many pharmaceuticals, natural products, and materials [ 5 , 6 , 7 , 8 ]. Consequently, various approaches to accomplish CDC reactions have been reported, including aza -Wacker [ 9 , 10 , 11 , 12 , 13 , 14 , 15 ] and transition-metal-catalyzed, directing-group-assisted reactions [ 16 , 17 , 18 , 19 ]. The nitrogen-centered, radical-mediated reaction is considered a powerful strategy for dehydrogenative C(sp 2 )–N bond formation, which proceeds via the addition of N-radical species to the π-system of arenes or alkenes, following recovery of the π-system by oxidation or elimination, because it can preclude the use of precious transition-metals or the introduction and removal of directing groups.…”

A Palladium-Catalyzed 4CzIPN-Mediated Decarboxylative Acylation Reaction of O-Methyl Ketoximes with α-Keto Acids under Visible Light

“…Inspired by these results, it was speculated that the indispensable oxidants such as excessive persulfate or silver salts may be replaced by using a photocatalyst with light, which would open a new, highly efficient pathway for decarboxylative reactions. Recently, our group presented several examples of oxime ether-directed selective C–H functionalization [ 13 , 14 , 15 ]. It is envisioned that when acetophenone oxime ether is employed as the substrate and benzoylformic acid as the source of benzoyl, the use of a photocatalyst under light may achieve direct ortho-selective benzoylation with a palladium catalyst.…”