Efficacy of Selenourea Organocatalysts in Asymmetric Michael Reactions under Standard and Solvent-Free Conditions

By varying the steric and electronic surroundings of the hydrogen-bonding motif, the novel chiral Cinchona-alkaloid based selenoureas were developed. Acting as bifunctional catalysts, they were applied in the Michael reactions of dithiomalonate and nitrostyrene providing chiral adducts with up to 96% ee. The asymmetric Michael–-hemiacetalization reaction of benzylidene pyruvate and dimedone, performed with the assistance of 5 mol% of selenoureas, furnished the product with up to 93% ee and excellent yields. The effectiveness of the new hydrogen-bond donors was also proved in solvent-free reactions under ball mill conditions, supporting the sustainability of the devised catalytic protocol.

The Influence of Hydrogen Bond Donors on the CO2 Absorption Mechanism by the Bio-Phenol-Based Deep Eutectic Solvents

Recently, deep eutectic solvents (DESs), a new type of solvent, have been studied widely for CO2 capture. In this work, the anion-functionalized deep eutectic solvents composed of phenol-based ionic liquids (ILs) and hydrogen bond donors (HBDs) ethylene glycol (EG) or 4-methylimidazole (4CH3-Im) were synthesized for CO2 capture. The phenol-based ILs used in this study were prepared from bio-derived phenols carvacrol (Car) and thymol (Thy). The CO2 absorption capacities of the DESs were determined. The absorption mechanisms by the DESs were also studied using nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and mass spectroscopy. Interestingly, the results indicated that CO2 reacted with both the phenolic anions and EG, generating the phenol-based carbonates and the EG-based carbonates, when CO2 interacted with the DESs formed by the ILs and EG. However, CO2 only reacted with the phenolic anions when the DESs formed by the ILs and 4CH3-Im. The results indicated that the HBDs impacted greatly on the CO2 absorption mechanism, suggesting the mechanism can be tuned by changing the HBDs, and the different reaction pathways may be due to the steric hinderance differences of the functional groups of the HBDs.

Reactive Deep Eutectic Solvents (RDESs): A New Tool for Phospholipase D-Catalyzed Preparation of Phospholipids

The use of Reactive Deep Eutectic Solvents (RDESs) in the preparation of polar head modified phospholipids (PLs) with phospholipase D (PLD)-catalyzed biotransformations has been investigated. Natural phosphatidylcholine (PC) has been submitted to PLD-catalyzed transphosphatidylations using a new reaction medium composed by a mixture of RDES/buffer. Instead of exploiting deep eutectic solvents conventionally, just as the reaction media, these solvents have been designed here in order to contribute actively to the synthetic processes by participating as reagents. RDESs were prepared using choline chloride or trimethyl glycine as hydrogen-bond acceptors and glycerol or ethylene glycol, as hydrogen-bond donors as well as nucleophiles for choline substitution. Specifically designed RDES/buffer reaction media allowed the obtainment of PLs with optimized yields in the perspective of a sustainable process implementation.

Octahedral Cobalt(III) Complex Based on Cheap 1,2-Phenylenediamine as a Bifunctional Metal-Templated Hydrogen Bond Donor Catalyst for Fixation of CO2 with Epoxides at Ambient Conditions

Hydrogen bond donors (HBD) are a sustainable privileged class of catalysts which are broadly used for the activation of compounds in synthetic chemistry. Among them, the metal-templated HBD complexes present...

Paradigm for efficient synthesis of bio-based polycarbonate with deep eutectic solvents as catalysts by inhibiting the degradation of molecular chains

In this study, an efficient catalytic system composed of deep eutectic solvents (DESs) was developed by adjusting the basicity of hydrogen bond donors (HBDs) to synthesize poly (isosorbide) carbonate (PIC)...