Driven by the inherent synthetic potential of CO2 as an abundant, inexpensive and renewable C1 chemical feedstock, the recent years have witnessed renewed interest in devising catalytic CO2 fixations into organic matter. Although the formation of C-C bonds via catalytic CO2 fixation remained rather limited for a long period of time, a close look into the recent literature data indicates that catalytic carboxylation reactions have entered a new era of exponential growth, evolving into a mature discipline that allows for streamlining the synthesis of carboxylic acids, building blocks of utmost relevance in industrial endeavors. These strategies have generally proven broadly applicability and convenient to perform. However, substantial challenges still need to be addressed reinforcing the need to cover metal-catalyzed carboxylation area in a conceptual and concise manner, delineating the underlying new principles that are slowly emerging in this vibrant area of expertise.

Transition-Metal-Catalyzed Carboxylation Reactions with Carbon Dioxide.

Carbon dioxide (CO2) has emerged as a sustainable, feasible, abundant one-carbon synthon and displays great potential in the synthesis of heterocycles such as lactones, lactams, and 2-oxazolidinones, which are privileged motifs in pharmaceutical chemistry demonstrating bioactivities. Although the fixation of CO2 is restricted due to its thermodynamic stability and kinetic inertness, multiple breakthroughs have been realized in annulation chemistry. This review concentrates on the advances made in the last five years in CO2-incorporated cyclization triggered by N-, O-, and C-nucleophiles. Three transformation modes of CO2 including carboxylative cyclization, carbonylative cyclization, and reductive cyclization have been summarized. Moreover, typical mechanisms and significant applications of these reactions are also described.

Recent advances in nucleophile-triggered CO2-incorporated cyclization leading to heterocycles.

A redox-neutral intermolecular dicarbofunctionalization of styrenes with CO2 at atmospheric pressure and carbon-centered radicals is described. This mild protocol results in multiple C-C bond-forming reactions from simple precursors in the absence of stoichiometric reductants, thus exploiting a previously unrecognized opportunity that complements existing catalytic carboxylation events.

/pdf/catalytic-intermolecular-dicarbofunctionalization-of-1vqddyb9ca.pdf

Catalytic Intermolecular Dicarbofunctionalization of Styrenes with CO2 and Radical Precursors.

The first thiocarboxylation of styrenes and acrylates with CO2 was realized by using visible light as a driving force and catalytic iron salts as promoters. A variety of important β-thioacids were obtained in high yields. This multicomponent reaction proceeds in an atom- and redox-economical manner with broad substrate scope under mild reaction conditions. Notably, high regio-, chemo-, and diasteroselectivity are observed. Mechanistic studies indicate that a radical pathway can account for the unusual regioselectivity.

Visible-Light-Driven Iron-Promoted Thiocarboxylation of Styrenes and Acrylates with CO2

Herein, we report a highly regio- and enantioselective copper-catalyzed reductive hydroxymethylation of styrenes and 1,3-dienes with 1 atm of CO2. Diverse important chiral homobenzylic alcohols were readily prepared from styrenes. Moreover, a variety of 1,3-dienes also were converted to chiral homoallylic alcohols with high yields and excellent regio-, enantio-, and Z/E-selectivities. The utility of this transformation was demonstrated by a broad range of styrenes and 1,3-dienes, facile product modification, and synthesis of bioactive compounds (R)-(−)-curcumene and (S)-(+)-ibuprofen. Mechanistic studies demonstrated the carboxylation of phenylethylcopper complexes with CO2 as one key step.

Highly Regio- and Enantioselective Copper-Catalyzed Reductive Hydroxymethylation of Styrenes and 1,3-Dienes with CO2.

The first direct use of carbon dioxide in the lactamization of alkenyl and heteroaryl C-H bonds to synthesize important 2-quinolinones and polyheterocycles in moderate to excellent yields is reported. Carbon dioxide, a nontoxic, inexpensive, and readily available greenhouse gas, acts as an ideal carbonyl source. Importantly, this transition-metal-free and redox-neutral process is eco-friendly and desirable for the pharmaceutical industry. Moreover, these reactions feature a broad substrate scope, good functional group tolerance, facile scalability, and easy product derivatization.

Lactamization of sp(2) C-H Bonds with CO2 : Transition-Metal-Free and Redox-Neutral.

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Lactamization of sp(2) C-H Bonds with CO2 : Transition-Metal-Free and Redox-Neutral.