Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

Abstract

The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species.

Non‐Oxidative Enzymatic (De)Carboxylation of (Hetero)Aromatics and Acrylic Acid Derivatives

“…The most commonly used pre‐activated substrates for transition metal‐catalyzed carboxylations include allylstannanes, organoboronic esters, organozinc reagents and aryl halides . Unsaturated compounds (olefins, allenes, alkynes) can be reductively carboxylated in a formal ‘hydrocarboxylation’ at the expense of a co‐reactant providing hydride species . The progress in organocatalytic and electrochemical methods further expands the scope of carbon dioxide fixation reactions in organic synthesis.…”

Enantioselective Incorporation of CO2: Status and Potential

“…methanol 3 ), as a sustainable carbon source. The number of efficient protocols for incorporation of CO2 is steadily growing, 4,5,6,7,8 however, little work has been devoted to making enantioselective reactions with CO2 [a general review of this area has been provided by Kleij and coworkers (2013) 9 and Lu (2016) 10 , and a specific review of stereoselective polymerization by Coates and coworkers (2014) 11 ]. It can be noted that both the carbon and the oxygen atoms of CO2 can be involved in the generation of novel chiral centres.…”

Carboxylation Reactions with Carbon Dioxide Using N‐Heterocyclic Carbene‐Copper Catalysts

“…Recently, transition metal‐catalyzed carboxylations of alkynes with CO 2 , such as hydrocarboxylation, alkylative/arylative carboxylation, and double carboxylation, have been developed as a straightforward protocol for the synthesis of α,β ‐unsaturated carboxylic acids . On the other side, the heterocarboxylation of alkynes with CO 2 can result in the simultaneous addition of both a heteroatom unit and a carboxylate group across the C−C triple bond, which emerges as a powerful method for the preparation of multifunctionalized alkenes.…”