Recent Strategies in Nickel-Catalyzed C–H Bond Functionalization for Nitrogen-Containing Heterocycles

Abstract

N-heterocycles are ubiquitous in natural products, pharmaceuticals, organic materials, and numerous functional molecules. Among the current synthetic approaches, transition metal-catalyzed C–H functionalization has gained considerable attention in recent years due to its advantages of simplicity, high atomic economy, and the ready availability of starting materials. In the field of N-heterocycle synthesis via C–H functionalization, nickel has been recognized as one of the most important catalysts. In this review, we will introduce nickel-catalyzed intramolecular and intermolecular pathways for N-heterocycle synthesis from 2008 to 2021.

Recent Advances in the Nickel-Catalyzed Alkylation of C-H Bonds

“…A related review covering Ni-catalyzed C-H bond functionalization reactions was reported [54]. The recent review specifically addressed intramolecular and intermolecular Ni-catalyzed functionalization reactions towards synthesis of N-containing heterocycles in the period 2008-2021 [54].…”

Ni-catalyzed unnatural prenylation and cyclic monoterpenation of heteroarenes with isoprene

“…Nitrogen containing cyclic compounds widely exist in various natural products and pharmaceutical molecules. The catalytic C-H functionalization of heterocycles [52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] is a straightforward and economic route to achieve post-modification of drugs and active molecules. And the introduction of dimethylallyl-related units (C5 skeletons) [71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88] into functional molecules often leads to dramatic changes in their lipophilicities and metabolic stabilities.…”

Ring Walking Mediated by Ni–Ni Species as a Vehicle for Enabling Distal C(sp2)–H Functionalization of Aryl Pivalates

“…Prompted by the seminal stoichiometric work of Kleiman and Dubeck, the recent years have witnessed significant progress in Ni-catalyzed C­(sp 2 )–H functionalization reactions. , Unlike other metals in the d 10 series, the reactivity of nickel catalysts in C­(sp 2 )–H functionalization remain predominantly confined to the utilization of proximal, yet strongly coordinating, directing groups, with bond formation occurring at the ortho position (Scheme , top) . Despite the advances realized, particularly in Catellani-type reactions, the means to enable distal C­(sp 2 )–H functionalization aided by Ni species without recourse to directing groups, acidic C­(sp 2 )–H bonds, or aryl halides still remains unexplored, particularly with phenol C–O derivatives as traceless entities (path b) …”