Critical view on the recent enantioselective synthesis of alcohols,amines and related molecules having tertiary benzylic stereocenter

Stereochemically defined enantioenriched molecules were, are and will always be playing a pivotal role in the development of novel pharmaceutical agents. On this line, compounds having tertiary benzylic stereocenter are of special note. This has led to an increase in the development of novel synthetic strategies for accessing molecules having this structural moiety. The current critical discussion proposes to describe the various synthetic methodologies for the enantioselective synthesis of diaryl methanols, diarylmethyl amines and other related scaffolds with tertiary benzylic stereogenic center that came up during 1995–2016. Through this critical view, we would not only like to give the readers a brief outlook on the different techniques that can be followed for the synthesis of a vast array of entities having this structural core, but also would like to highlight the limitations the protocols that need to be addressed.     

Processing and properties of sintered submicron IR transparent alumina derived through sol–gel method

For the first time, sintered alumina with high transparency in mid infrared region, composed of submicron grains, has been fabricated using sol–gel processing. Commercially available boehmite powder was used to prepare the stable sol. The sol was mixed with appropriate amount of sintering aids and alumina seeds. The sol was further gelled, dried, and heat treated at 1000?°C for producing alumina powder. The powder was further shaped into pellets by compaction and sintered at temperatures between 1200 and 1400?°C in air. Sintered samples were further pressed hot isostatically to produce sintered submicron transparent alumina. The synthesized powder was characterized for its morphology and phase. The sintered and hot isostatically pressed samples were characterized for their physical, mechanical, and optical properties. The present method produced transparent alumina with transparency upto 87% in mid-wave infrared region. These transparency values were at par with the transparency of single crystal sapphire in the mid-wave infrared region and the hardness values were even superior than sapphire.

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Nanoisozymes: Crystal‐Facet‐Dependent Enzyme‐Mimetic Activity of V2O5 Nanomaterials

Nanomaterials with enzyme‐like activity (nanozymes) attract significant interest owing to their applications in biomedical research. Particularly, redox nanozymes that exhibit glutathione peroxidase (GPx)‐like activity play important roles in cellular signaling by controlling the hydrogen peroxide (H₂O₂) level. Herein we report, for the first time, that the redox properties and GPx‐like activity of V₂O₅ nanozyme depends not only on the size and morphology, but also on the crystal facets exposed on the surface within the same crystal system of the nanomaterials. These results suggest that the surface of the nanomaterials can be engineered to fine‐tune their redox properties to act as “nanoisozymes” for specific biological applications.     

Two‐Dimensional Fullerene Assembly from an Exfoliated van der Waals Template

Two‐dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom‐up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C₆₀ as a polymerizable monomer. The C₆₀ building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C₆₀ monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C₆₀. The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid.     

Gene Expression on DNA Biochips Patterned with Strand‐Displacement Lithography

Lithographic patterning of DNA molecules enables spatial organization of cell‐free genetic circuits under well‐controlled experimental conditions. Here, we present a biocompatible, DNA‐based resist termed “Bephore”, which is based on commercially available components and can be patterned by both photo‐ and electron‐beam lithography. The patterning mechanism is based on cleavage of a chemically modified DNA hairpin by ultraviolet light or electrons, and a subsequent strand‐displacement reaction. All steps are performed in aqueous solution and do not require chemical development of the resist, which makes the lithographic process robust and biocompatible. Bephore is well suited for multistep lithographic processes, enabling the immobilization of different types of DNA molecules with micrometer precision. As an application, we demonstrate compartmentalized, on‐chip gene expression from three sequentially immobilized DNA templates, leading to three spatially resolved protein‐expression gradients.     

Hypochlorite‐Mediated Modulation of Photoinduced Electron Transfer in a Phenothiazine–Boron dipyrromethene Electron Donor–Acceptor Dyad: A Highly Water Soluble “Turn‐On” Fluorescent Probe for Hypochlorite

A highly water‐soluble phenothiazine (PTZ)–boron dipyrromethene (BODIPY)‐based electron donor–acceptor dyad ( WS‐Probe ), which contains BODIPY as the signaling antennae and PTZ as the OCl^? reactive group, was designed and used as a fluorescent chemosensor for the detection of OCl^?. Upon addition of incremental amounts of NaOCl, the quenched fluorescence of WS‐Probe was enhanced drastically, which indicated the inhibition of reductive photoinduced electron transfer (PET) from PTZ to ¹BODIPY*; the detection limit was calculated to be 26.7 nm . Selectivity studies with various reactive oxygen species, cations, and anions revealed that WS‐Probe was able to detect OCl^? selectively. Steady‐state fluorescence studies performed at varied pH suggested that WS‐Probe can detect NaOCl and exhibits maximum fluorescence in the pH range of 7 to 8, similar to physiological conditions. ESI‐MS analysis and ¹H NMR spectroscopy titrations showed the formation of sulfoxide as the major oxidized product upon addition of hypochlorite. More interestingly, when WS‐Probe was treated with real water samples, the fluorescence response was clearly visible with tap water and disinfectant, which indicated the presence of OCl^? in these samples. The in vitro cell viability assay performed with human embryonic kidney 293 (HEK 293) cells suggested that WS‐probe is non‐toxic up to 10 μm and implicates the use of the probe for biological applications.     

Synthesis,characterization, and antimicrobial studies of some palladium complexes with an octamethyl tetraazacyclotetradecadiene ligand and isomers of its reduced form

Biologically important tetraaza-macrocyclic ligand 3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene dihydroperchlorate, Me₈[14]diene·2HClO₄ (L₁·2HClO₄) was synthesized by the condensation of 1,2-diaminopropane with acetone in presence of quantitative amount of HClO₄ and three isomeric ligands designated as L_A, L_B and L_C were separated by the reduction of L₁·2HClO₄ with NaBH₄ and fractional crystallization from xylene. The nitrato, nitro, bromido, and iodido complexes of palladium with diene ligand L₁ were prepared by the interaction of L₁·2HClO₄ with K₂[Pd(NO₃)₄], K₂[Pd(NO₂)₄], K₂[PdBr₄], and K₂[PdI₄] (prepared by the reactions with PdCl₂ with KNO₃, KNO₂, KBr, and KI, respectively), respectively. The bromide and iodido complexes of L_A were prepared by the axial substitution reactions with [PdL_ACl₂]Cl₂. By contrast, similar complexes of other isomeric ligands L_B and L_C were prepared by axial addition reactions of [PdL^?][PdCl₄] (L′?=?L_B or L_C) with KBr and KI, respectively. The complexes were characterized on the basis of elemental analysis: IR, ¹H-NMR, UV–Vis spectroscopic analysis, and magnetic and molar conductivity data. The antifungal and antibacterial activities of these compounds have been studied against some phyto-pathogenic fungi and bacteria.     

Supramolecular Gels Derived from the Salts of Variously Substituted Phenylacetic Acid and Dicyclohexylamine: Design,Synthesis, Structures,and Dye Adsorption

A well‐studied supramolecular synthon, namely, secondary ammonium monocarboxylate (SAM), was exploited to generate a new series of organic salts derived from variously substituted phenylacetic acid and dicyclohexylamine as potential low‐molecular‐weight gelators. As much as 25 % of the SAM salts under study were gelators. The gels were characterized by rheology, and the morphology of the gel networks was studied by high‐resolution electron microscopy. Single‐crystal and powder XRD data were employed to study structure–property (gelation) correlations. One of the gels could adsorb a hydrophobic dye (Nile Red) more efficiently than that of a hydrophilic dye (Calcein) from dimethyl sulfoxide; this might provide useful clues towards the development of stain‐removing gels.     

Mixture Design PARAFAC HPLC-DAD Metabolomic Fingerprints of Fractionated Organic and Basic Extracts from <Emphasis Type="Italic">Erythrina speciosa</Emphasis> Andrews Leaves

HPLC-DAD analysis of statistical mixture design extracts of Erythrina speciosa Andrews leaves provided chromatographic and UV–visible profiles of their basic and organic fractions that were treated with the PARAFAC multivariate method. The design extracts provided greater varieties and amounts of metabolites than could be obtained by classical extraction methods. Fractionation provided more diverse fingerprint information than obtained previously from only the crude extract. The two largest chromatographic peaks, one with a 4.8 min elution time having an intense spectral band at 235 nm and the other a 5.8 min peak with an intense 238 nm band for the basic fraction were obtained with the ternary 1:1:1 ethanol–dichloromethane–hexane mixture. These can be assigned to diene-type and lactonic alkaloids. Peaks with the same retention times are also found in the organic fraction but are extracted with different mixtures and have distinct spectral behavior in the 235 nm region, probably being aromatic alkaloids. The above strategy permits a more unambiguous assignment of metabolic groups to specific chromatographic peaks. This can be expected to provide higher quality chromatographic fingerprints for natural products’ chemistry.