Search Results (5)

One-component or bifunctional organocatalysts are some of the most capable compounds to perform the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO₂) since the presence of a co-catalyst is not required. In this study, we designed, synthesized, and evaluated five halogenated compounds as bifunctional organocatalysts for this catalytic transformation. Among them, 1,3-dimethylimidazolium iodide (1) exhibited the highest catalytic efficiency, enabling the synthesis of a broad range of monosubstituted cyclic carbonates with diverse functional groups under mild conditions (80 °C, 20 bar CO₂) within 1 h, using only 1 mol% catalyst loading. Remarkably, this organocatalyst also facilitated the synthesis of five internal cyclic carbonates and a carvone-derived exo-cyclic carbonate, which was obtained for the first time without the use of a metal catalyst, under more demanding conditions. A mechanistic proposal was developed through a combination of ¹H-NMR studies and density functional theory (DFT) simulations. Styrene oxide and cyclohexene oxide were used as model substrates to investigate the reaction pathway, which was computed using an optimized climbing-image nudged elastic band (CI-NEB) method. The results revealed the critical role of 1,3-dimethylimidazolium iodide in key reaction steps, particularly in facilitating the epoxy ring opening process. These findings highlight the potential use of bifunctional compounds as efficient and versatile catalysts for CO₂ valorization. Full article

In the past few decades, N-heterocyclic carbenes (NHCs) have opened the new field of organocatalysis in synthetic organic chemistry. This review highlights the dramatic progress in the field of NHC-catalyzed C–O bond formation based on the activation of aldehyde C(sp²)–H bonds. The oxidative and redox transformations for the synthesis of various molecules with structural diversity and complexity are summarized. Furthermore, new methods and strategies for NHC catalysis are emerging continuously; thus, cooperative catalysis with Brønsted acid, hydrogen-bonding catalyst, transition-metal catalyst, and photocatalyst are also described. Full article

A one-pot multicomponent green process is investigated for the synthesis of perfluoroalkylated cyclic carbonate which merges the photo-promoted Atom Transfer Radical Addition (ATRA) of a perfluoroalkyl iodide (Rf-I) onto allyl alcohols with the Lewis-base-promoted carboxylative cyclization. The evolution of the complex mixture during the reaction was monitored by in situ ATR-IR and Raman spectroscopies that provided insights into the reaction mechanism. The effect on the kinetics and the carbonate yields of key parameters such as the stoichiometry of reagents, the nature of the Lewis base and the solvent, the temperature and the pressure were evaluated. It was found that high yields were obtained using strong Lewis bases that played both the role of activating the allyl alcohol for the generation of the allyl carbonate in the presence of CO₂ and promoting the ATRA reaction through the activation of C₄F₉I by halogen bonding. This protocol was also extended to various unsaturated alcohols. Full article

α-Aminonitriles, which have anticancer, antibacterial, antiviral, and antifungal properties, have played an important role in pharmacology. Furthermore, they can also be used to synthesize natural and unnatural amino acids. The main bottleneck in the commercialization of these products is their large-scale production with controlled chirality. A variety of methods have been used to synthesize α-aminonitriles. Among other reported methods for preparing α-aminonitriles, the Strecker reaction is considered appropriate. Recent developments, however, have enabled the α-cyanation of tertiary and secondary amines by functionalizing the carbon–hydrogen (C–H) bond as an attractive alternative procedure for the preparation of α-aminonitriles in the presence of an oxidant and a cyanide source. In most cases, these reactions are catalyzed by transition metal catalysts, such as Fe, Cu, Rh, V, Au, Ru, Mo, Pt, Re, and Co, or by photocatalysts. As an alternative, organocatalysts can also be used to produce aminonitriles. Although there have been numerous reviews on the preparation of α-aminonitriles, no such reviews have been published specifically on the organocatalyzed synthesis of α-aminonitriles. Organocatalysis plays a significant role in synthesizing α-aminonitriles via Strecker-type reactions and cross dehydrogenative coupling reactions (CDC). In this mini review, we discuss the organocatalyzed synthesis of these molecules. A review of new organocatalysts for the synthesis of aminonitriles is expected to provide insight into the development of new industrial catalysts. Full article

Room temperature ionic liquids (RTILs) have been widely used as (co)solvents in several catalytic processes modifying, in most of the cases, the catalyst activity and/or the selectivity for the studied reactions. However, there are just a few examples of their use in hydrogen bonding organocatalysis. In this paper, we show the positive effect of a set of imidazole-based ionic liquids ([bmim]BF₄ and [hmim]PF₆) in the enantioselective addition of formaldehyde tert-butylhydrazone to prochiral α-keto esters catalyzed by a sugar-based chiral thiourea. Reactions performed in the presence of low percentages of RTILs led to an increase of the catalyst activity, thereby making possible to work at lower temperatures. Thus, the chiral tert-butyl azomethyl tertiary alcohols could be obtained with moderate to good conversions and higher enantioselectivities for most of the studied substrates when using up to 30 vol% of [hmim]PF₆ as a cosolvent in processes performed in toluene. Full article