Supramolecular chemistry of liquid-liquid extraction.

Liquid-Liquid Extraction (LLE) is a venerable and widely used method for the separation of a targeted solute between two immiscible liquids. In recent years, this method has gained popularity in the supramolecular chemistry community due to the development of various types of synthetic receptors that effectively and selectively bind specific guests in an aqueous medium through different supramolecular interactions. This has eventually led to the development of state-of-the-art extraction technologies for the removal and purification of anions, cations, ion pairs, and small molecules from one liquid phase to another liquid phase, which is an industrially viable method. The focus of this perspective is to furnish a vivid picture of the current understanding of supramolecular interaction-based LLE chemistry. This will not only help to improve separation technology in the chemical, mining, nuclear waste treatment, and medicinal chemistry sectors but is also useful to address the purity issue of the extractable species, which is otherwise difficult. Thus, up-to-date knowledge on this subject will eventually provide opportunities to develop large-scale waste remediation processes and metallurgy applications that can address important real-life problems.

Selective recognition and extraction of iodide from pure water by a tripodal selenoimidazol(ium)-based chalcogen bonding receptor.

A selenium-based tripodal chalcogen bond (ChB) donor TPI-3Se is demonstrated for the recognition and extraction of I- from 100% water medium. NMR and ITC studies with the halides reveal that the ChB donor selectively binds with the large, weakly hydrated I-. Interestingly, I- crystallizes out selectively in the presence of other halides supporting the superiority of the selective recognition of I-. The X-ray structure of the ChB-iodide complex manifests both the µ1 and µ2 coordinated interactions, which is rare in the C-Se···I chalcogen bonding. Furthermore, to validate the selective I- binding potency of TPI-3Se in pure water, comparisons are made with its hydrogen and halogen bond donor analogs. The computational analysis also provides the mode of I- recognition by TPI-3Se. Importantly, this receptor is capable of extracting I- from pure water through selenium sigma-hole and I- interaction with a high degree of efficiency (∼70%).

Pd-Catalyzed Tandem Pathway for Stereoselective Synthesis of (E)-1,3-Enyne from ß-Nitroalkenes by Using a Sacrificial Directing Group.

The involvement of nitroalkenes instead of minimal one alkyne motif for (E)-1,3-enynes synthesis through a palladium catalyzed stereoselective bond forming pathway at room temperature is presented. Implication of nitro group as a sacrificial directing group, formation of magical alkyne on a newly developed Csp 3 -Csp 3 bond with initial palladium-MBH adduct make this methodology distinctive. This protocol features an unprecedented sequential acetate addition, carbon-carbon bond formation, isomerization of double bond and nitromethane degradation in a tandem catalytic walk via dancing hybridization. Mechanistic understanding through identification of intermediates and computational calculations furnishes complete insight into the tandem catalytic pathway. Broad substrates scope and functional groups tolerance make this synthetic methodology magnificent and dynamic. This represents the first example of stereoselective 1,3-enyne synthesis exclusively from alkene substrates by introducing the concept of sacrificial directing group.

Room-Temperature Synthesis of 1,3,5-Tri(het)aryl Benzene from Nitroalkenes Using Pd(OAc)2: Complete Mechanistic and Theoretical Studies.

Herein, a room-temperature catalytic pathway for 1,3,5-tri(het)aryl derivatives from nitroalkenes using simple Pd(OAc)2 is presented. This newly developed C-C bond-forming methodology takes place in a cascade manner with the initial pallado-Morita-Baylis-Hillman (MBH) type adduct. The broad substrate scopes, functional group tolerance, and different aryl-substituted benzene derivatives make this methodology more attractive. Furthermore, the mechanistic understanding through isolation of intermediates and DFT studies of the catalytic cycle provide requisite insight into the methodology.