Advances in Transition Metal-Catalyzed Carbonylation Reactions for α,β-Unsaturated Carbonyls: Applications, Challenges, and Opportunities.

Over the past two decades, transition metal-catalyzed carbonylative reactions have revolutionized the synthesis of α,β-unsaturated carbonyl compounds. These innovative, atom-economic transformations elegantly incorporate CO moiety into readily available substrates as well as complex molecules to produce a wide array of valuable compounds, including carboxylic acids, esters, ketones, amides, aldehydes, and cyclic carbonyls. These versatile products have immense applications in material science, pharmaceuticals, agrochemicals, and fine chemicals. This review aims to summarize and critically highlight the recent advancements in the carbonylation process for the synthesis of α,β-unsaturated carbonyl compounds including a detailed description of mechanisms and comprehensive functional group compatibility. Additionally, the challenges in the relevant domain such as selectivity, catalyst efficiency, and scalability as well as exploring the exciting potential for its future development have been covered. We hope this review will serve as a convenient reference for the last 15 years in the field of carbonylation reactions for α,β-unsaturated carbonyl compounds using a variety of transition metal catalysts and carbon monoxide (or its surrogates) as C1 source.