Nickel-catalyzed C–O/N–H, C–S/N–H, and C–CN/N–H annulation of aromatic amides with alkynes: C–O, C–S, and C–CN activation

Abstract

The Ni-catalyzed reaction of ortho-phenoxy-substituted aromatic amides with alkynes in the presence of LiOtBu as a base results in C–O/N–H annulation with the formation of 1(2H)-isoquinolinones.

Nickel‐Catalyzed Suzuki‐Miyaura Cross‐Coupling Involving C−O Bond Activation

“…We report herein on a Ni‐catalyzed Suzuki‐Miyaura cross‐coupling that involves the activation of a C−O bond, in which an amidate anion functions as a directing group. The present protocol using an amidate directing group is a promising strategy for activating various strong bonds, such as C−O, C−F, C−CN, and C−S bonds [9–12] . Studies directed to the use of this methodology are currently underway and will be reported in due course.…”

“…Encouraged by this reaction, we were prompted to apply this protocol to the activation of other unreactive bonds. Surprisingly, the strategy was found to be applicable to the activation of other unreactive bonds, such as C−F, [9] C−O, C−S, and C−CN [10] . In all cases, no ligand was required.…”

Nickel-Catalyzed C–F/N–H Annulation of 2-(2-Fluoroaryl) N-Heteroaromatic Compounds with Alkynes: Activation of C–F Bonds

“…This strategy is a promising method for the activation of C-F bonds 4 as well as other unreactive bonds, such as C-O, C-S, and C-CN. 8 Investigations on the further use of this methodology for the activation of unreactive bonds are currently underway and will be reported in due course. 1 H and 13 C NMR spectra were recorded on a JEOL ECZ-400 spectrometer; samples were dissolved in CDCl 3 with tetramethylsilane as an internal reference standard.…”

Nickel‐Catalyzed Csp2−OMe Functionalization for Chemoselective Aromatic Homologation En Route to Nanographenes

“…[6] On the other hand, C sp2 À OPh bond activation have been recently engaged into Ni-catalyzed CÀ O/NÀ H annulation of aromatic amides with alkynes for the production of isoquinolinones, by using C sp2 À OPh substrates bearing Nphenyl-benzamide directing groups (Figure 1b). [7] Concerning the mechanism of C sp2 À OMe activation, it is generally believed that oxidative addition at nickel(0) species is the key step in the process, although current knowledge is still limited. [8] In addition to the oxidative addition mechanism, non-classical modes of activation should be taken into account depending on the nature of the nucleophile and the ligand used.…”