Directed Amination of Non‐Acidic Arene CH Bonds by a Copper–Silver Catalytic System

Abstract

Amine meets arene: A method for direct amination of β‐C(sp2)H bonds of benzoic acid derivatives and γ‐C(sp2)H bonds of benzylamine derivatives has been developed. The reaction is catalyzed by Cu(OAc)2 and a Ag2CO3 cocatalyst, and shows high generality and functional‐group tolerance, as well as providing a straightforward means for the preparation of ortho‐aminobenzoic acid derivatives.

Cobalt-Promoted Dimerization of Aminoquinoline Benzamides

“…8,10a–c Other research groups have extensively used these auxiliaries for palladium-, ruthenium-, iron-, and copper-catalyzed reactions. 9 The aminoquinoline auxiliary can direct cobalt-catalyzed C–H activation/alkene, alkyne, and CO migratory insertion sequences, leading to ortho -functionalized benzoic acid derivatives.…”

Nickel-Catalyzed C–H Bond Functionalization Utilizing an N,N′-Bidentate Directing Group

“…These directing groups are easily converted to other synthetically useful functional groups. Deprotection of an 8-aminoquinline moiety to carboxylic acids was easily achieved by hydrolysis under acidic conditions Scheme 27 Ni-catalyzed thiolation of C-H bonds with diaryl sulfides Nickel-Catalyzed C-H Bond Functionalization Utilizing an N,N (Scheme 30a) [56] or basic conditions [57] (Scheme 30b). The 8-aminoquinoline moiety was removed by treatment with HCl in refluxing methanol [58] or BF 3 •Et 2 O in methanol at 100 C to give the corresponding ester [59].…”

Copper-Mediated Intermolecular C–H/C–H and C–H/N–H Couplings via Aromatic C–H Cleavage

“…Benzamides bearing the quinoline moiety are directly aminated under the copper/silver bimetallic catalyst system, although the exact role of the silver salt is not clear (Eq. 31) [57]. The oxazoline-based double coordination strategy allows the otherwise difficult dehydrogenative C-N coupling of various heteroarenes and heteroarylamines to afford heteroatom-rich diarylamines of pharmaceutical importance (Eq.…”