Nickel-Catalyzed Reaction of Benzamides with Bicylic Alkenes: Cleavage of C–H and C–N Bonds

Abstract

The nickel-catalyzed reaction of aromatic amides that contain an 8-aminoquinoline as a directing group with bicyclic alkenes, such as norbornene and 1,4-dihydro-1,4-epoxynaphthalene, results in the cleavage of both the C−H bond at the ortho-position of the benzene ring and the C(O)−N bond to give methanofluoren-9-one and 1,4-epoxyfluoren-9-one derivatives. Both Ni(OTf) 2 and Ni(cod) 2 show a high catalytic activity. The presence of AgOAc is essential for the reaction to proceed. In the meta-substituted aromatic amides, a less hindered C−H bond is exclusively functionalized.

Palladium‐Catalyzed Annulation of Acyl Fluorides with Norbornene via Decarbonylation and CO Reinsertion

“…Heteroaromatic 1 i and 1 j also reacted with norbornene ( 2 ) to afford heterocyclic ketones 11 and 12 . These products have not been synthesized in previously reported work using acyl chlorides or amides (entries 7 and 8). On the other hand, several aroyl fluorides, such as 4‐chlorobenzoyl fluoride, 4‐nitrobenzoyl fluoride, 2‐methylbenzoyl fluoride, 2‐methoxybenzoyl fluoride, or 1 H ‐indole‐3‐carbonyl fluoride, did not provide the corresponding ketones.…”

Emerging Nickel Catalysis in Ketones Synthesis Using Carboxylic Acid Derivatives

“…In this transformation, Ni(II) catalyst was actively participated in both events and delivered cyclic ketones 116 and 117 up to 91 % yield (B, Scheme 10). [47b] Next, amides derived from pyrroles ( 118 ) [48a] and amidazoles ( 121 ) [48b] i. e. amide‐4 were also investigated for CCR with aryl, heteroaryl boronates ( 119 ) and alkyl/aryl/heteroaryl bromides ( 122 ) respectively and furnished ketones ( 120 and 123 ) in excellent yield (C and D, Scheme 10). Notably, pyrrolic amides 118 worked under Ni(COD) 2 and bis‐NHC ligand catalytic system while amidazoles 121 worked with both NiI 2 and Ni(COD) 2 in presence of metallic zinc.…”

Transition metal-catalyzed coupling of heterocyclic alkenesviaC–H functionalization: recent trends and applications

“…190 The Chatani group developed the synthesis of epoxybenzofluorenone through the coupling of benzamide with heterobicyclic alkenes (Scheme 130). 191 8-Aminoquinoline chelation assistance is necessary, and the addition of excess AgOAc (6 equiv.) plays a valuable role in the removal of 8-aminoquinoline since it inhibits the catalytic activity of Ni(OTf ) 2 .…”