Synthesis and applications of copillar[5]arene dithiols

Abstract

A novel copillar[4+1]arene incorporating alkylthiol substituents was synthesised in three steps and structurally characterised as the first example of a pillar[n]arene to incorporate two terminal thiols on the same aromatic ring. The macrocycle was attached to gold electrodes through a standard dipping technique. Cyclic voltammetry demonstrated selectivity for Li⁺ over other alkali metal cations. The copillar[4+1]arene was also used as a capping agent in the preparation of 3 nm gold nanoparticles.     

Synthesis,Characterization and Photocatalytic Activity of Ag+‐ and Sn2+‐Doped KTi0.5Te1.5O6

In this study, the photocatalytic dye degradation efficiency of KTi_0.5Te_1.5O₆ synthesized through solid‐state method was enhanced by cation (Ag⁺/Sn⁺²) doping at potassium site via ion exchange method. As prepared materials were characterized by XRD, SEM‐EDS, IR, TGA and UV–Vis Diffuse reflectance spectroscopic (DRS) techniques. All the compounds were crystallized in cubic lattice with space group. The bandgap energies of parent, Ag⁺‐ and Sn⁺²‐doped KTi_0.5Te_1.5O₆ materials obtained from DRS profiles were found to be 2.96, 2.55 and 2.40 eV, respectively. Photocatalytic efficiency of parent, Ag⁺‐ and Sn⁺²‐doped materials was evaluated against the degradation of methylene blue (MB) and methyl violet (MV) dyes under visible light irradiation. The Sn⁺²‐doped KTi_0.5Te_1.5O₆ showed higher activity toward the degradation of both MB and MV dyes and its higher activity is ascribed to the lower bandgap energy compared to the parent and Ag⁺‐doped KTi_0.5Te_1.5O₆. The mechanistic degradation pathway of methylene blue (MB) was studied in the presence of Sn²⁺‐doped KTi_0.5Te_1.5O₆. Quenching experiments were performed to know the participation of holes, super oxide and hydroxyl radicals in the dye degradation process. The stability and reusability of the catalysts were studied.     

Multi-catalysis reactions: direct organocatalytic sequential one-pot synthesis of highly functionalized cyclopenta[b]chromen-1-ones

We have developed a new technology called multi-catalysis for the sequential one-pot synthesis of highly functionalized heterocycles. A practical and novel multi-component aniline-, self- and Br?nsted acid-catalyzed selective process for the sequential one-pot synthesis of highly substituted 2-(2-hydroxy-aryl)-cyclopentane-1,3-diones, 3,9-dihydro-2H-cyclopenta[b]chromen-1-ones and 3,3-dimethyl-2,3,4,9-tetrahydro-xanthen-1-ones is reported. Direct combination of aniline- and self-catalyzed cascade olefination-hydrogenation (O-H) and Br?nsted acid-catalyzed cascade oxy-Michael-dehydration (OM-DH) of 1,3-diones, salicylic aldehydes and organic-hydrides is developed in one-pot to furnish the highly functionalized 3,9-dihydro-2H-cyclopenta[b]chromen-1-ones and 3,3-dimethyl-2,3,4,9-tetrahydro-xanthen-1-ones with high yields.     

Facile One‐Pot Multicomponent Synthesis of β‐Acetamido Ketones with Amberlyst‐15 as Heterogeneous Catalyst

The one‐pot multicomponent coupling of an aromatic aldehyde, an enolizable ketone or keto ester, acetonitrile, and acetyl chloride at room temperature in the presence of Amberlyst‐15 as catalyst affords β‐acetamido ketones in high yields. The inexpensive catalyst works under heterogeneous conditions and can be readily reused.     

Double cascade reactions based on the Barbas dienamine platform: highly stereoselective synthesis of functionalized cyclohexanes for cardiovascular agents

The amino acid proline catalyzed the three- and five-component cascade olefination-Diels-Alder-epimerization and olefination-Diels-Alder-epimerization-olefination-hydrogenation reactions of readily available precursors enones 1a-i, arylaldehydes 2a-k, alkyl cyanoacetates 3a-e and Hantzsch ester 9 to furnish highly substituted prochiral 1-cyano-4-oxo-2,6-diaryl-cyclohexanecarboxylic acid alkyl esters 6 and 1-cyano-4-(cyano-alkoxycarbonyl-methyl)-2,6-diaryl-cyclohexanecarboxylic acid alkyl esters 10 in a highly diastereoselective fashion with excellent yields. Prochiral cis-isomers 6 are excellent starting materials for the synthesis of cardiovascular agents and hypnotic active products.     

pi-Conjugated macrocycles from thiophenes and benzenes

pi-Conjugated macrocycles consisting of thiophenes and benzenes exhibit benzenoid features for 4npi macrocycles, whereas (4n + 2)pi macrocycles are annulenoid due to rapid interconversion between quinoid and Kekule canonical forms in the benzene units.     

Total synthesis and stereochemical confirmation of manassantin A, B, and B1

Stereocontrolled total syntheses of manassantins A, B, and B1 and saucerneol are described for the first time based on a novel cycloetherification of end-differentiated benzylic alcohols as a common intermediate. [structure: see text].     

Cu(OTf)2/Cu-catalyzed four-component reaction: a facile synthesis of α-alkoxytriazoles via click chemistry

Aldehyde, alcohol, azide, and alkyne undergo smooth coupling by means of acetal formation, azidation, and a subsequent ‘click reaction’ in the presence of copper(II) triflate and copper metal in acetonitrile to furnish α-alkoxy-1,2,3-triazoles in good yields. The method provides a convenient route to prepare a wide range of triazoles in a one-pot operation via a four-component reaction.     

Ligand dependence of the synthetic approach and chiroptical properties of a magic cluster protected with a bicyclic chiral thiolate

Chiral gold clusters stabilised by enantiopure thiolates were prepared, size-selected and characterised by circular dichroism and mass spectrometry. The product distribution is found to be ligand dependent. Au(25) clusters protected with camphorthiol show clear resemblance of their chiroptical properties with their glutathionate analogue.     

Simple and one-pot protocol for synthesis of indene-spiro-oxindoles involving tandem Prins and Friedel-Crafts reactions

[reaction: see text] A simple and one-pot protocol for the synthesis of indene-spiro-oxindole derivatives via TiCl4-mediated reaction between 1,1-diarylethylenes and isatin derivatives involving construction of two carbon-carbon bonds through tandem Prins and intramolecular Friedel-Crafts (PFC) reactions has been described. A plausible mechanism for this transformation is also presented.