C–H Functionalization of Aromatic Amides

Abstract

Since the beginning of the 21st century, significant progress has been made in transition metal‐catalyzed C–H functionalization of aromatic amides. The achievements in this field have mainly focused on ortho (proximal) functionalization, there have been far fewer reports on remote C–H functionalization, and para‐ and meta‐selective functionalizations remain a major challenge. Interestingly, there are few related comments in this field. In a few published cases, the scope of the report is relatively narrow, either to comment on the functionalization of a specific directing group or to summarize the functionalization of a specific reaction site. Herein, for the first time, we have comprehensively summarized the C–H functionalization of aromatic amides. This review is divided into three parts: ortho‐, para‐ and meta‐C–H functionalization of aromatic amides, and is subdivided according to the type of catalyst. The directing groups, reaction types, conditions, mechanism and applications of the corresponding reactions are discussed in detail.

Chemodivergence made possible by micellar photocatalysis: C-H arylation vs. N-dealkylation of chlorinated benzamides in aqueous media

“…Control experiments have shown that a photocatalyst is necessary and proved the superiority of methylene blue (2a) over such common mediators as rhodamine 6G (4), [Ir(ppy)2(dtbbpy)]PF6 (5) or strongly reducing 10-phenylphenothiazine (3) (Table 1, entries 2-5). CTAB can be replaced by other surfactants e.g.…”

“…The functionalization of benzamide structures, due to their presence in various compounds of biological or functional importance, remains a vibrant area of synthetic chemistry. [1][2][3] While the modifications within the aromatic ring or carbonyl group are well developed, [4,5] the repertoire of reactions occurring at N-alkyl substituents is limitted (Scheme 1a). It includes C-H activation followed by cyclization to isoindoline -a processes, which requires harsh reaction conditions such as the use of lithium diisopropylamide, [6,7] t-BuOK, [8] or stoichiometric amounts of tetrabutylammonium persulfate and TEMPO [9] .…”

Recent Advancement in the Copper Mediated Synthesis of Heterocyclic Amides as Important Pharmaceutical and Agrochemicals

“…There are some reports in the literature reviews for the catalytic and enzymetic routes for amidation reactions [24–33] . Furthermore, there are few reports on the application of heterocyclic amides in medicine and agriculture [34–36] .…”

Merging Cu-catalysed C–H functionalisation and intramolecular annulations: computational and experimental studies on an expedient construction of complex fused heterocycles

“…11 Current research in our group focuses on the development of protocols for rapid access to heterocyclic compounds through the use of cheap and readily available benzamide starting compounds, using C-H functionalisation as the key tool, 12,13 a field which is attracting a lot of attention. 14 One method to potentially and easily achieve even higher molecular complexity is to include the coupling partner as part of the substrate, thus operating through an intramolecular approach and providing the opportunity for Double Annulation Reactions (DAR's). In this context, a novel route towards fused dihydrobenzofuran-dihydroisoquinolone compounds from benzamides with tethered olefins, operating through a DAR approach, was reported independently by the groups of Rovis and Glorius in late 2013/early 2014 utilising relatively expensive rhodium catalysts (Scheme 1b).…”