ortho‐Acylation of Aryl Iodides Enabled with Imides via Palladium/Norbornene/CuI Catalysis

Abstract

Herein, a three component Catellani-type reaction catalyzed by the Palladium/Norbornene/ CuI (Pd/NBE/CuI) cooperative system by using Nacylph-thalimides as acyl electrophiles is reported, which gives access to a series of aromatic ketones. The transformation is performable in the presence of water, albeit with decreased reaction yield. The additive CuI was crucial to facilitate the cleavage of C(O)À N bond of imide. This protocol showed broad substrate scope: both alkyl and aryl acyl groups could be installed at the ortho-position of aryl iodides; alkenes and boronic acids can be used as termination reagents.

Direct Synthesis of C4-Acyl Indoles via C–H Acylation

“…Following Dong’s first breakthrough in the ortho C–H amination of iodobenzene in 2013, the Luan group combined ortho C–H amination with cyclization dearomatization in 2017 . Dong, Gu, and Liang independently reported on the ortho C–H acylation of iodobenzene in 2015 simultaneously . In 2019, the Luan group achieved ortho C–H acylation and alkylation of iodobenzene through a four-component series reaction .…”

“…Therefore, one of the main challenges is delicately regulating the reaction activity between the acylation reagent and the amine to avoid undesired side reactions, in order to attain selective C–H acylation in the synthesis of C4-acyl indoles (Scheme e). In the past few years, further research by the Gu , and Sun ,, groups on C–H acylation reagents has provided us with new ideas to address this challenging problem (Scheme c).…”