Pd-catalyzed bidentate auxiliary assisted remote C(sp³)–H functionalization

Abstract

This article presents “state of art” trends in achieving the bidentate auxiliary assisted distal sp3 C–H functionalization beyond proximal sites. The substrate scope and mechanistic underpinnings of the key methodologies are highlighted.

Transition‐Metal‐Catalyzed Remote C(sp3)−H Functionalization Of Carboxylic Acid And Its Derivatives

“…Transition metal catalysis has revolutionized CÀ H functionalization and in particular late transition metals, such as palladium, [18,24,35,39,59] ruthenium, [60,61] rhodium, [62,63] iridium, [64,65] gold, [66][67][68][69] and platinum, [70,71] have exhibited powerful catalytic efficiencies. These transition metals react first with the CÀ H bonds in a process called CÀ H activation [30,72] to produce a reactive CÀ M bond, which is further converted to new functional groups under mild conditions leading to a highly stepand atom-economical process.…”

Silver Ions Promoted Palladium-Catalyzed Inactive β-C(sp3)–H Bond Arylation in Batch and Continuous-Flow Conditions

“…Pd­(II) catalysts have been widely studied for the inactive C­(sp 3 )–H bond functionalization . The coordinating partner of a certain substrate may lead to the creation of a variety of pharmaceutically significant motifs.…”

Expedient Ni-catalyzed C–H/C–H cross-dehydrogenative coupling of aryl amides with azoles

“…4 However, the positional-selective functionalization remains an appealing yet a significant challenge owing to the omnipresence of C–H bonds in organic molecules. The implementation of the directing group (DG) strategy, 5,6 which consists of a coordinating site that directs the metal centre into the close proximity of a specific C–H bond and thereby facilitates the selective cleavage, has thus witnessed remarkable advancements in recent years and led to sought-after strategies for C–C bond formations using (hetero)arenes. 7 Furthermore, being a first-row transition metal, Ni( ii )-catalyzed or mediated C–H functionalization has attracted considerable attention due to its minimal toxicity and earth-abundance.…”