Metal Complexes Catalyzed Cyclization with CO2

Abstract

This chapter describes in general terms the catalytic methodology that has been made available for the use of carbon dioxide (CO 2 ) in cyclization reactions that incorporate an intact CO 2 fragment without changing the formal oxidation state of the carbon center. The major focus of this chapter will be on the most successful organometallic/inorganic complexes that have been used as catalyst systems throughout the last decade and the preferred ligand frameworks leading to elevated reactivity and/or selectivity behavior in CO 2 coupling reactions. Attention will be especially given to homogeneous catalyst systems as they have proven to be more versatile in CO 2 conversion catalysis and often have modular characteristics that allow for optimization of structure-activity relationships. The most important reactions that have been studied in the current context are designated CO 2 "addition" reactions to small molecule heterocycles such as epoxides and aziridines, though more recently other coupling partners such as diamines, dialcohols, and amino nitriles have further advanced the use of CO 2 in organic synthesis providing access to a wider range of structures. This chapter will serve to demonstrate the utility of CO 2 as a carbon reagent in the catalytic formation of the most prominent organic structures using cyclization strategies specifically.

A novel 2,5-furandicarboxylic acid-based bis(cyclic carbonate) for the synthesis of biobased non-isocyanate polyurethanes

“…The bromo-alkoxide then attacks the carbon atom of CO 2 to produce ve-membered cyclic carbonate rings. 26,27 In this reaction, the reactant and the catalyst were soluble in dichloromethane, while the bis(cyclic carbonate) was not. Therefore, a simple washing and drying procedure could be used for product separation and catalyst recycling.…”

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

“…Unlike other reviews for similar means, the purpose of this article is to focus on the most recent advances for preparing carboxylic acid derivatives from unsaturated hydrocarbon backbones using Ni as well as the cheaper and more abundant Fe species in a homogeneous 45 Page 2 of 38 Top Curr Chem (Z) (2016) 374:45 manner, including mechanistic considerations, when appropriate. Therefore, other catalytic CO 2 functionalization processes of paramount importance such as the area of cyclic carbonates [19][20][21], polymer formation, production of methanol or formic acid [22][23][24], electrochemical methods [25], co-catalyzed carboxylations [26], carbonylation methods [27], or reductive carboxylations of organic (pseudo)halides [14-16, 28, 29], among others, are beyond the scope of this review.…”

Delineation of the Critical Parameters of Salt Catalysts in the N‐Formylation of Amines with CO2

“…Ionic liquids( ILs) and other simples alts are promising catalysts for an umber of CO 2 related applications including the synthesis of cyclic carbonates, [2][3][4] quinazolinediones, [5,6] oxazolidinones, [7,8] N-methylamines, [9] N-formylamines [10,11] and other compounds. [12][13][14] Synthetic modification of the cation and/or anion allows an ear-infinite number of salts to be prepared, [15,16] whiles imultaneously allowing their performance to be tuned for ad esired application.H owever,t he design of more efficient salt catalysts is frequently hampered by limited mechanistic understanding and incomplete structure activity relationships, in part due to al ack of benchmark reactionc onditions.…”