Synthesis of Five‐ and Six‐Membered Benzocyclic Ketones through Intramolecular Alkene Hydroacylation Catalyzed by Nickel(0)/N‐Heterocyclic Carbenes

Abstract

Transition-metal-catalyzed hydroacylation has been accepted as a promising synthetic method to form carbon-carbon bonds between an aldehyde and unsaturated compounds, such as alkenes, alkynes, and ketones. A number of catalyst systems have been developed, and high enatio-, regio-, and chemo-selectivity has been achieved.[1] Despite these extensive efforts and praiseworthy results, an inevitable side reaction persists: decarbonylation from an acyl metal intermediate, which causes a decrease in atom-efficiency and a deactivation of the catalyst through the coordination of carbon monoxide (Scheme

Nickel N-heterocyclic carbene complexes and their utility in homogeneous catalysis

“…[90,109]. A bipyridyl bridged dinuclear complex (277) [90] was prepared from (198) reacting with 4,4'−bipyridine in the presence of AgPF 6 (Scheme 16 and Figure 19). …”

Regioselective Hydroacylation of 1,3-Dienes by Cobalt Catalysis

“…Our study contributes to the emerging strategies available for hydroacylation via non-precious-metal catalysis. 13,15 …”

Direct Functionalization of C−H Bonds by Iron, Nickel, and Cobalt Catalysis

“…2017, 23,9206 -9232 www.chemeurj.org Review [Ni(cod) 2 ]a nd aL ewis acid (usually AlMe 3 ), paving the wayf or the developmento fn ickel-catalyzed hydrocarbamoylation of alkenes and alkynes. [54] The group of Cramer furtherr eported an asymmetric variant of this class of reactions, ar arec atalytic enantioselective CÀHa ctivation report in the nickel literature so far (Scheme 14, 80!81). [55] Their system hinges on the synergistic action of ac hiral diaminophosphine oxide (SPO) and the Lewis acid promoter to enable formationo fa"linked bimetallicspecies" (82).…”