Valorization of the Primary Building Blocks Ammonia and Acetone Featuring Pd- and Ni-Catalyzed Monoarylations

Abstract

This review describes recent progress that has been made in the monoarylation of ammonia and acetone. More specifically, the application of ferrocenyl bisphosphine ligands has enabled significant progress in substrate scope and reaction conditions as well as catalyst costs and availability. Herein these advancements are compared with previous systems, including the (commercial) availability of the corresponding catalyst systems.

Exploration of Aryl Phosphates in Palladium-Catalyzed Mono-α-arylation of Aryl and Heteroaryl Ketones

“…α-Arylated carbonyl motifs are commonly found in natural products and pharmaceutically active molecules . Palladium-catalyzed α-arylation of carbonyl compounds is one of the most powerful and attractive methodologies for the construction of C­(sp 3 )–C­(sp 2 ) bonds to access these valuable products . Since the research groups of Miura, Buchwald, and Hartwig independently disclosed their findings on palladium-catalyzed α-arylation of ketones, substantial efforts have been made to advance this technology, including fine-tuning ligands, precatalysts, and other reaction parameters. , …”

“…To address this challenging circumstance, it is important to develop a general and active catalyst system. In the past decade, state-of-the-art ligands have been developed and selected for tackling the electrophiles that are considered to be extremely difficult, such as aryl chlorides, tosylates, and mesylates in palladium-catalyzed α-arylation of ketones. ,, As a continuation of our research interest in the development of phosphine ligands and their application in α-arylation using challenging electrophiles, ,, this paper presents the first palladium-catalyzed α-arylation of aryl and heteroaryl ketones with aryl phosphates (Scheme B).…”

Synform Issue 2021/03

“…While the arylation of carbonyl compounds with transition metal catalysts, via the formation of enolate intermediates, represents a powerful and relatively well-established class of carbon-carbon bond-forming reactions, 1 the transposition of this technology to simple acetone has remained -in comparisonrather elusive. 2 For example, this challenging transformation has rarely been achieved using palladium catalysis with aryl halide electrophiles. "From an economic viewpoint, the development of this methodology with more sustainable and cost-effective nickel catalysts appeared as a very valuable alternative, but the transposition to nickel has proven highly challenging," remarked Professor Abderrahmane Amgoune, from CNRS & Université Lyon 1 (Villeurbanne, France).…”

Nickel‐Catalyzed Tandem Reaction of Functionalized Arylacetonitriles with Arylboronic Acids in 2‐MeTHF: Eco‐Friendly Synthesis of Aminoisoquinolines and Isoquinolones

“…Nickel, as af irst-row transition-metal in the same group as that of palladium, has attracted significant attention due to its low cost and abundance,m eeting the requirementsf or sustainable chemicals ynthesis. [6] Despite the remarkable success of nickelcatalyzed transformationsu sing alkyne with CCb ond as the substrate, [7] nickel-catalyzed nitrile insertion reactions have not been extensively documented. [8] The development of nickelcatalyzed addition of organoboron reagents to nitriles has remained ag reat challenge due to the lack of reactivity of the inert CNb onds and the competing side reaction.…”