Camphor-derived thioureas: Synthesis and application in asymmetric Kabachnik-Fields reaction

A series of camphor-derived thiourea organocatalysts 3a–f were designed and synthesized from(1R,3S)-camphoric acid 1 and applied to the one-pot three-component Kabachnik–Fields reaction. Catalyst 3c was found to be an efficient organocatalyst for the reaction of 2-cyclopropylpyrimidin-4-carbaldehyde 4,various amines 5, and diphenylphosphite 6 to yield the corresponding enantioselective a-aminophosphonates 7a–e in 74%–82% yields and 14%–35% ee.     

Organic Brønsted acid-catalyzed cycloadditions of o-quinone methides with 1, 3-dicarbonlys: Facile access to xanthenones and chromanones

The in-situ generation of o-quinone methides and their inverse-electron-demand Diels–Alder reaction in the presence of pentacarboxycyclopentadiene—an organic Brønsted acid—has been reported. The synthesis of xanthenones and chromanones in good to excellent yields from the [4 + 2] cycloaddition of quinone methides with 1, 3-dicarbonyls and Meldrum's acid has been accomplished. The development of this method helps in generating a number of biologically potent heterocycles with medicinal applications.     

The monitoring of nucleotide diphosphate kinase activity by blue native polyacrylamide gel electrophoresis

Nucleoside diphosphate kinase (NDPK) has been shown to play a pivotal role in modulating a plethora of cellular processes. In this study, we report on a blue native (BN) PAGE technique which allows the facile assessment of NDPK activity and expression. The in-gel detection of NDPK relies on the precipitation of formazan at the site of immobilized enzyme activity. This is achieved by coupling the formation of ATP, as a consequence of gamma-phosphate transfer from NTP to ADP, to hexokinase (HK), glucose-6-phosphate dehydrogenase (G6PDH), oxidized nicotinamide adenine dinucleotide phosphate (NADP), phenazine methosulfate (PMS), and iodonitrotetrazolium chloride (INT). 2-D denaturing gel analysis confirmed that the activity bands corresponded to NDPK as indicated by subunit composition. Furthermore, the sensitivity and specificity of this readily accessible procedure was assessed by monitoring the in-gel activity of NDPK using different concentrations of GTP and CTP as well as deoxynucleoside triphosphates. This electrophoretic technique allows the quick and easy detection of NDPK, a housekeeping enzyme crucial to cell survival.     

Synthesis and antimicrobial activity of N‐substituted N′‐[6‐methyl‐2‐oxido‐1,3,2‐dioxaphosphinino(5,4‐b)pyridine‐2‐yl]ureas

N‐Substituted N′‐[6‐methyl‐2‐oxido‐1,3,2‐dioxaphosphinino(5,4,‐b)pyridine‐2‐yl]ureas have been accomplished by condensation of equimolar quantities of chlorides of various carbamidophosphoric acids ( 3 ) with 3‐hydroxyl‐6‐methyl‐2‐pyridinemethanol (lutidine diol) ( 4 ) in the presence of triethylamine in dry toluene–tetrahydrofuran (1:1) mixture at 45–50°C. Their structures were established by elemental analyses, IR, ¹H NMR, ¹³C NMR, and ³¹P NMR spectral data. Their antifungal and antibacterial activity is also evaluated. Most of these compounds exhibited moderate antimicrobial activity in the assays. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:509–512, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10181     

Two biologically active thio­phene‐3‐carbox­amide derivatives

The two title compounds, 2‐({(1Z)‐[4‐(di­methyl­amino)phenyl]methylene}amino)‐4,5‐dimethyl‐N‐(2‐methylphenyl)thiophene‐3‐carboxamide, C₂₃H₂₅N₃OS, (I), and 2‐({(1E)‐[4‐(dimethylamino)phenyl]methylene}amino)‐N‐(4‐methylphenyl)‐4,5,6,7‐tetrahydro‐1‐benzothiophene‐3‐carboxamide,C₂₅H₂₇N₃OS, (II), show antibacterial and antifungal activities. The asymmetric unit of (II) contains two crystallographically independent mol­ecules. The o‐toluidine ring in (I) lies gauche with respect to the thio­phene ring. In (II), the p‐toluidine ring is coplanar with the thio­phene ring in one mol­ecule, but is tilted from it in the other mol­ecule. Neither structure exhibits any significant intermolecular interactions, but in both, an intramolecular N—H⋯N hydrogen bond forms a pseudo‐six‐membered ring, thus locking the molecular conformation and removing conformational flexibility.     

Quantum chemical and master equation study of OH + CH2O → H2O + CHO reaction rates in supercritical CO2 environment

We investigated the reaction rates of OH + CH₂O → H₂O + CHO at CO₂ pressures of up to 1000 atm with and without CO₂ molecule included in a reactive complex. Both mechanisms begin with formation of the hydrogen-bonded prereactive complexes. Our ab initio calculations indicate a possibility of catalytic effect, predicting an activation barrier that one order of magnitude lower when the CO₂ molecule is involved. To verify this effect, we use the Rice–Ramsperger–Kassel–Marcus theory and solve unimolecular master equations in the steady-state approximation. We assume the equilibrium between prereactive complexes and reactants and compare the bimolecular reaction rates for the two mechanisms. The catalyzed reaction mechanism is found to be faster at higher CO₂ pressures and lower temperatures, when prereactive complexes have nonnegligible concentration. Therefore, this catalytic effect may be important for this reactive process in room temperature supercritical CO₂ solvent, but is unlikely to play a role during oxy-combustion.     

Synthesis,antibacterial activity,and docking studies of some novel N′-benzylidene-2-(2,4,5-trifluorophenyl)acetohydrazides

Research on Chemical Intermediates - An improved method was developed for synthesis of 2,4,5-trifluorobenzohydrazide derivatives through condensation of trifluorophenylacetohydrazide with different...     

Phosphomolybdic acid promoted Kabachnik–Fields reaction: an efficient one-pot synthesis of α-aminophosphonates from 2-cyclopropylpyrimidine-4-carbaldehyde

2-Cyclopropylpyrimidin-4-yl-aryl/benzothiazole derived α-aminophosphonates were synthesized in a simple and efficient method from a three-component condensation reaction of 2-cyclopropylpyrimidin-4-carbaldehyde, various anilines/benzothiazole amines, and different phosphites by using 0.5 mol % of phosphomolybdic acid (PMA, H₃PMo₁₂O₄₀) in dichloromethane at room temperature in good to excellent yields with short reaction times.     

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an SNAr‐Based “Aromatic Metamorphosis” of Thiaarenes

Dibenzothiophene dioxides, which are readily prepared through oxidation of the parent dibenzothiophenes, undergo nucleophilic aromatic substitution with anilines intermolecularly and then intramolecularly to yield the corresponding carbazoles in a single operation. The “aromatic metamorphosis” of dibenzothiophenes into carbazoles does not require any heavy metals. This strategy is also applicable to the synthesis of indoles. Since electron‐deficient thiaarene dioxides exhibit interesting reactivity, which is not observed for that the corresponding electron‐rich azaarenes, a combination of a thiaarene‐dioxide‐specific reaction with the S_NAr‐based aromatic metamorphosis allows transition‐metal‐free construction of difficult‐to‐prepare carbazoles.