Catalytic CH Amination with Aromatic Amines

Abstract

Aniline joins the club: A β-diketiminato copper(I) catalyst enables C-H amination of anilines employing low catalyst loadings to preclude oxidation to the diazene ArN=NAr. Electron-poor anilines are particularly resistant towards diazene formation and participate in the amination of strong and unactivated C-H bonds. N-alkyl anilines also take part in C-H amination.

Metal‐Free Preparation of Cycloalkyl Aryl Sulfides via Di‐tert‐butyl Peroxide‐Promoted Oxidative C(sp3)H Bond Thiolation of Cycloalkanes

“…[5] However, C(sp 3 )–H bond activation of cycloalkanes to form C–C, [6] C–O, [7] C–N [8] bonds still has not been well reported because C(sp 3 )–H bond activation of cycloalkanes is more difficult than C(sp 3 )–H bond activation adjacent to heteroatoms, double bonds, phenyl or electron withdrawing groups. Li and others have done elegant work in this field using a transition-metal catalyst (such as Ru, Sc, Fe, etc.)…”

Efficient synthesis of 2-arylquinazolines via copper-catalyzed dual oxidative benzylic CH aminations of methylarenes

“…On the basis of the above results and the previous reports [39][40][41][42][43][44][45][46][47][48][49][50], a plausible catalytic cycle of this transformation is proposed (Scheme 2). Initially, the coordination of 1a to one Cu II species and subsequent ligand exchange generates the copper complex A, which forms the benzyl/Cu II species B by benzylic C-H activation.…”

“…Recently, transition-metal-catalyzed oxidative aminations of sp 3 C-H bond have emerged as important methods for C-N bond formations because of short steps and atom-economical advantages [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38]. In particular, copper as an inexpensive and lowly toxic metal catalyst, has been employed to catalyze the formation of C-N bond via a sp 3 C-H amination [39][40][41][42][43][44][45][46][47][48][49]. For instance, copper-catalyzed cascade coupling of 2-halobenzaldehyde with acetamidine hydrochloride (or benzaldehyde) to construct C-N bond was reported [53][54].…”

Binuclear β-diketiminate complexes of copper(i)

“…[3][4][5][6][7][8][9][10][11][12][13][14][15] Warren and coworkers have expanded the oxidation chemistry of copper(I) β-diketiminate complexes to include diazoalkanes, PhI=NTs, organoazides and tert-butylperoxide. [16][17][18][19][20][21][22][23][24][25][26][27][28] These stoichiometric studies are part of a broader programme, developing exciting synthetic protocols for the functionalization of carbon-hydrogen bonds in hydrocarbons. The catalytic generation of a monomeric copper nitrene intermediate and its transformation to a copper(II) amide by hydrogen atom abstraction has been proposed as a key step in the transformation of carbon-hydrogen bonds to carbon-nitrogen bonds.…”

“…The catalytic generation of a monomeric copper nitrene intermediate and its transformation to a copper(II) amide by hydrogen atom abstraction has been proposed as a key step in the transformation of carbon-hydrogen bonds to carbon-nitrogen bonds. 20,[22][23][24]26 Similarly, a copper(II) alkoxide is proposed as a crucial intermediate during the oxidation of cyclohexane to tert-butyl-cyclohexyl ether by tert-butylperoxide in the presence of a copper(I) diketiminate complexes. 25 In more recent years, the chemistry of copper β-diketiminate has been expanded to include both dinucleating and trinucleating ligands.…”