First-Row Transition-Metal-Catalyzed Carbonylative Transformations of Carbon Electrophiles

Abstract

The main contributions in the field of first-row transition-metal-catalyzed (base-metal-catalyzed) carbonylative transformations have been summarized and discussed. The contents have been divided according to the electrophiles applied, followed by the different types of nucleophiles. Their reaction mechanisms and applications have been emphatically discussed.

Palladium-catalyzed oxidative dehydrogenative carbonylation reactions using carbon monoxide and mechanistic overviews

“…In the presence of a transition metal catalyst, reactions of electrophiles, nucleophiles, and carbon monoxide result in carbonylative coupling reactions (Scheme 1b). 5,6 This type of carbonylation reaction has been demonstrated as a direct strategy for the synthesis of various carbonyl-containing compounds and their derivatives. However, these reactions require pre-functionalized substrates, for example, aromatic halides or triflates as electrophiles, and boronic acids or zinc reagents as nucleophiles.…”

“…In the past decade, palladium catalysis has played a major role in oxidative dehydrogenative carbonylation. 6,8,9 This review focuses on the research progress achieved in recent years within the area of palladium-catalyzed oxidative dehydrogenative carbonylation.…”

Nickel‐catalyzed aminocarbonylation of aryl halides with carbamoylsilanes: efficient synthesis of secondary (primary) aromatic amides

“…So numerous alternate protocols have been explored. Among reported methods, palladium–catalyzed aminocarbonylation is a powerful method for the synthesis of aryl amides starting from aryl halides, amines and carbon monoxide, and is most frequently use reaction in organic synthesis . Although this method offers the advantage of functional group tolerance, it suffers from the troublesome handling of hazardous carbon monoxide gas, and the reaction setup requiring high–pressure reactors and harsh reaction conditions .…”

Palladium‐Catalyzed Carbonylative Coupling of Aryl Iodides with Alkyl Bromides: Efficient Synthesis of Alkyl Aryl Ketones

“…[6a] Comparably, base metals have shown better activity in carbonylation of alkyl halides. [7] For example, Mankad's group has recently developed a Cu/Mn bimetallic system that enables the carbonylative Suzuki-Miyaura coupling of alkyl halides. [8] Despite having many advantages, the main drawback of these methods is that the organometallic compounds need to be pre-prepared, which sometimes limits their application.…”