A General Method for Aminoquinoline-Directed, Copper-Catalyzed sp² C–H Bond Amination

Abstract

An operationally simple and general method for copper-catalyzed, aminoquinoline-assisted amination of β-C(sp2)-H bonds of benzoic acid derivatives is reported. The reaction employs Cu(OAc)2 or (CuOH)2CO3 catalysts, an amine coupling partner, and oxygen from air as a terminal oxidant. Exceptionally high generality with respect to amine coupling partners is observed. Specifically, primary and secondary aliphatic and aromatic amines, heterocycles, such as indoles, pyrazole, and carbazole, sulfonamides, as well as electron-deficient aromatic and heteroaromatic amines are competent coupling components.

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

“…[171] 6.2.5. [173][174][175][176][177][178][179][180][181][182][183][184][185][186] Theu tility of an 8aminoquinoline moiety for the Rh-catalyzed functionalization of amides discussed here was mainly reported by Chatani and co-workers in terms of various alkylation and alkenylation reactions. [172] Thee ase of installation and removal of the 8- aminoquinoline moiety enhances the utility of its usage in synthetic chemistry and many groups have focused their studies on this directing group.…”

Directing‐Group‐Assisted Transition‐Metal‐Catalyzed Direct Intermolecular C−H Amidation and Amination of Arenes

“…In addition, the 8‐aminoquinoline auxiliary could be smoothly deprotected by base hydrolysis. Furthermore, by employing pyridine as solvent, oxygen from the air could be used as a terminal oxidant instead of NMO . Very recently, Punniyamurthy extended the amino source to include various aromatic azoles, such as pyrroles, indoles, pyrazoles, and carbazoles.…”

Nickel‐Catalyzed Electrooxidative C−H Amination: Support for Nickel(IV)

“…[10] Despite this indisputable progress, electrochemical CÀHn itrogenationw ith the less toxic base metal nickel [11,12] has thus far provene lusive. As ad irect consequence,w ithin our program [13] on nickel-catalyzed [14] CÀHa ctivation, [15] we becamea ttractedt op robing the opportunities of joining nickel catalysis with electrochemical CÀHa ctivation, the results of which we report herein. Key features of our findings include a) first nickel-catalyzed electrochemicalC ÀHa minations, b) chemicalo xidant-free CÀHn itrogenationsw ith cyclic and more challenging acyclica mines,a nd c) key mechanistic insights into nickel-electrocatalyzed CÀHa ctivation.…”

“…It is noteworthy that an additional redox-mediator was not required for the nickel-catalyzed electroamination,c ontrasting with very recent coppercatalysis. [14] With the catalytic conditions being optimized, we next probedt he effect exertedb yt he N-substituent of benzamides 1 (Scheme 1). Hence, various N,N-coordination modes (4-7), and an N,O-bidentate chelation (8)m et with limited success, clearly contrasting with ac obalt catalysis manifold.…”