Synthesis of 1-Azabenzanthracene: Epimerization with the Use of 1,3-Dihydrobenzo(c)thiophene -S,S Dioxide as a Source of ortho-Quinodimethane

The cycloaddition of o-quinodimethane, from 1,3-dihydrobenzo(c)-S,S dioxide, to 5,6-dihydroquinoline yields a mixture of adducts isomeric at the newly created ring junction. The cycloadducts can be dehydrogenated to the fully aromatic 1-azabenzanthracene.     

Reduction of Azobenzenes to Diphenylhydrazines

A selective, rapid and simple reduction of azobenzenes to diphenylhydrazines using borane-THF is described.     

Syntheses and structures of novel heteroarene-fused coplanar pi-conjugated chromophores

We have synthesized a series of novel coplanar chromophores in which heteroarenes, namely, thiophene, benzothiophene, and carbazole, were fused to neighboring phenylene ring(s) through intramolecular annulation via sp(3)-hybridized carbon atoms bearing two p-tolyl groups as peripheral substituents. The molecular configurations of the pi-conjugated backbones were determined by X-ray crystallographic analysis; the heteroarene-fused molecular frameworks of these novel molecules exhibit nearly coplanar conformations. [structure: see text]     

Highly Enantioselective Formation of α‐Allyl‐α‐Arylcyclopentanones via Pd‐Catalysed Decarboxylative Asymmetric Allylic Alkylation

A highly enantioselective Pd‐catalysed decarboxylative asymmetric allylic alkylation of cyclopentanone derived α‐aryl‐β‐keto esters employing the (R,R)‐ANDEN‐phenyl Trost ligand has been developed. The product (S)‐α‐allyl‐α‐arylcyclopentanones were obtained in excellent yields and enantioselectivities (up to >99.9 % ee). This represents one of the most highly enantioselective formations of an all‐carbon quaternary stereogenic center reported to date. This reaction was demonstrated on a 4.0 mmol scale without any deterioration of enantioselectivity and was exploited as the key enantioselective transformation in an asymmetric formal synthesis of the natural product (+)‐tanikolide.     

First Total Synthesis of N‐(3‐Guanidinopropyl)‐2‐(4‐hydroxyphenyl)‐2‐oxoacetamide

The first total synthesis of the α‐oxo amide‐based natural product, N‐(3‐guanidinopropyl)‐2‐(4‐hydroxyphenyl)‐2‐oxoacetamide ( 3 ), isolated from aqueous extracts of hydroid Campanularia sp., has been achieved. The α‐oxo amide 12 , prepared via the oxidative amidation of 1‐[4‐(benzyloxy)phenyl]‐2,2‐dibromoethanone ( 9a ) with 4‐{[(tert‐butyl)(dimethyl)silyl]oxy}butan‐1‐amine ( 10a ), has been used as the key intermediate in the total synthesis of 3 as HBr salt. On the way, an expeditious total synthesis of polyandrocarpamide C ( 2c ), isolated from marine ascidian Polyandrocarpa sp., was carried out in four steps.     

Whole‐Cell Photoenzymatic Cascades to Synthesize Long‐Chain Aliphatic Amines and Esters from Renewable Fatty Acids

Long‐chain aliphatic amines such as (S,Z)‐heptadec‐9‐en‐7‐amine and 9‐aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole‐cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf‐ATA), and a photoactivated decarboxylase from Chlorella variabilis NC64A (Cv‐FAP) in a one‐pot process. In addition, long chain aliphatic esters such as 10‐(heptanoyloxy)dec‐8‐ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively, by using the combination of the ADH, a Baeyer–Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv‐FAP. The target compounds were produced at rates of up to 37 U g^?1 dry cells with conversions up to 90 %. Therefore, this study contributes to the preparation of industrially relevant long‐chain aliphatic chiral amines and esters from renewable fatty acid resources.     

Coherent Solution‐phase Synthesis of a Germanium‐Graphitic Nanocomposite and Its Evaluation for Lithium‐Ion Battery Anodes: Non‐innocent Role of the Mashima Reagent

The organosilicon reagent 1,4‐bis‐(trimethylsilyl)‐1,4‐diaza‐2,5‐cyclohexadiene 2 plays the binary role of the simultaneous reduction of GeCl₂.dioxane 1 dissolved in oleylamine to Ge nanocrystals and the formation of graphitic sheets under hot‐injection conditions. This colloidal synthetic route to germanium nanocrystals embedded on N‐doped graphitic nanosheets Ge/NG is free of any template or catalyst and involves easy purification techniques. The Ge/NG/C obtained after carbonization has been explored for anode performance in lithium‐ion batteries. Both Ge/NG and Ge/NG/C can be obtained on a gram scale and are bottleable under argon for months.     

A Convenient Synthesis of Hindered N-Aryl Substituted Cyclic Amines

An efficient and high yielding synthesis of N-substituted pyrrolidines and piperidines is described.     

Preparation, structural analysis and dielectric properties of Bi x La1−x FeO3 perovskite

Rare earth element substituted bismuth ferrites (BiFeO₃) are of enormous importance as magnetoelectric materials. The polycrystalline samples of Bi _x La_1−x FeO₃ (x=0, 0.2, 0.4, 0.6, 0.8) were prepared by solid-state reaction using standard ceramic method. The single-phase formation of these compounds was confirmed by X-ray diffraction (XRD) studies. The samples with x=0, 0.2, 0.4, 0.6 are found to be orthorhombic while the sample with x=0.8 is triclinic. The dielectric constant (ε′) and dissipation factor (tan δ) were measured in the frequency range 100 Hz to 1 MHz at room temperature and as a function of temperature at certain fixed frequencies (1 kHz, 10 kHz, 100 kHz, 1 MHz). All the samples showed dielectric dispersion. The dielectric constant with temperature shows a broad peak; the peak temperature shifts with frequency which reflects the relaxor-type behavior. The peak above 600 K in the measured temperature range corresponds to antiferromagnetic ordering temperature (Néel temperature). The broadness of the peak changes with composition. The ac conductivity as well as ε′ are found to be maximum for the sample x=0.2 at room temperature.     

Magnetoelectric effect in cobalt ferrite-barium titanate composites and their electrical properties

CoFe₂O₄-BaTiO₃ composites were prepared using conventional ceramic double sintering process with various compositions. Presence of two phases in the composites was confirmed using X-ray diffraction. The dc resistivity and thermoemf as a function of temperature in the temperature range 300 K to 600 K were measured. Variation of dielectric constant (ɛ′) with frequency in the range 100 Hz to 1 MHz and also with temperature at a fixed frequency of 1 kHz was studied. The ac conductivity was derived from dielectric constant (ɛ′) and loss tangent (tan δ). The nature of conduction is discussed on the basis of small polaron hopping model. The static value of magnetoelectric conversion factor has been studied as a function of magnetic field.