An Update on Oxidative C–H Carbonylation with CO

Abstract

Carbonyl derivatives widely exist in pharmaceuticals, agricultural chemicals, materials, and natural products. Developing novel, efficient, and green carbonylation methods represent one of the hottest research topics in organic synthesis, not only for academics but also for the chemical industry. Carbon monoxide (CO) turns out to be the most ideal carbonyl source because of its 100% atomic efficiency and low price. Meanwhile, compared with “classical” cross-coupling between nucleophiles and electrophiles, oxidative cross-coupling, which uses nucleophiles as reactants under oxidation conditions, has received increasing attention during the past two decades. Among oxidative carbonylation, the C–H functionalization/carbonylation is undoubtedly one of the most atom- and step-economical methods. Due to its great potential in green synthesis, this field has grown vigorously over the past decade, and many strategies have been developed, including transition metal catalysis, photoredox catalysis, electrochemical protocol, and so on. Since our last review of oxidative carbonylation in 2011, the C–H bond carbonylation has attracted continuous attention and undergone extensive development. Therefore, it is time to update this important field.

Concise synthesis of 2,3-disubstituted quinoline derivatives via ruthenium-catalyzed three-component deaminative coupling reaction of anilines, aldehydes and amines

“…The carbon KIE results indicate the deamination (C–N bond cleavage) as the turnover-limiting step, while an apparent lack of electronic effects from para -substituted benzaldehydes suggests that the C–C bond formation is not likely involved in the rate-limiting step of the coupling reaction. While the proposed pathway shares similar mechanistic features with the recently published Povarov-type of coupling reactions, 22 the proposed pathway illustrates new mechanistic insights on the catalytically relevant intermediate species as well as the role of Ru catalyst on mediating the deaminative coupling reaction.…”

Highly regioselective C–H carbonylation of alkenes with phenyl formateviaaryl to vinyl 1,4-palladium migration

“…4 As C–H activation grows by leaps and bounds, 5 transition-metal-catalyzed C–H carbonylation has attracted much attention due to its efficiency and atom economy. 6 In this field, the synthesis of α,β-unsaturated carbonyl compounds with high stereoselectivity is still a challenging task. Notably, the inherent steric properties of the reaction substrates were often utilized to solve this challenge.…”

A Facile synthesis of Biaryl ketones in recyclable system: Triazenes as new coupling partners in the carbonylative Suzuki and Hiyama cross‐coupling reactions using NFSac as CO source

“…Carbon monoxide (CO) had crossed several phases for its extensive applications in various fields, right from the fear concerning its toxicity to essential biological roles [1] . Carbonylation is a process which refers to the introduction of either one or two molecules of carbon monoxide into the substrates to result carbonyl compounds, [2a–c] amides, [2d–e] carbamates, [2f–h] carboxylic acids, [2i–j] acyl fluorides, [2k–l] esters, [2m–n] ketoesters [2o] and their derivatives [2p–r] etc. Using various metal catalysts for this reactions Ni, [3a–d] Fe, [3e–g] Cu, [3h–i] Co, [3j–k] Rh, [3l–m] Ru [3n–o] and etc.…”