Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas

Abstract

We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing the expedient construction of unsymmetric dialkyl ketones with broad functional group tolerance. The leverage of a newly developed NN 2 -pincer type ligand enables the chemoselective three-component carbonylation by overcoming the competing Negishi coupling, the undesired β-hydride elimination, and dehalogenation of alkyl iodides side pathways. Both alkyl iodides and alkyl tosylates are compatible in the single electron transfer involved mechanism.K etones are prevalent skeletons in various natural products, pharmaceuticals, and materials, which can also undergo a

Photoredox-catalyzed carbonylative acylation of styrenes with Hantzsch esters

“…9 Among the various achievements, very recently, Chen and co-workers described a novel nickel-catalyzed carbonylation of unactivated alkyl halides with organozinc reagents to yield a variety of alkyl ketones in good yields in general. 10…”

Nickel/Photoredox-Catalyzed Carbonylative Cross-Electrophile Coupling of Organohalides and Carboxylic Acid Esters with Phenyl Formate

“…Since the pioneering carbonylative coupling reaction by Heck in 1974, transition metal-catalyzed carbonylative coupling reactions have emerged as one of the most powerful and practical methods through incorporation of a carbonyl group (C=O) into readily available building blocks . Nevertheless, conventional carbonylative reactions are often requiring presynthesized organometallic reagents and toxic carbon monoxide (CO) gas or metal carbonyl reagents as the carbonyl sources (Scheme a, left) . In recent years, reductive cross-electrophile coupling utilizing earth abundant transition metals (e.g., Ni, Co) has achieved increasing attention to mitigate the aforementioned issues .…”