Mild, General, and Regioselective Synthesis of 2-Aminopyridines from Pyridine N-Oxides via N-(2-Pyridyl)pyridinium Salts

A synthesis of 2-aminopyridines from pyridine N-oxides via their corresponding N-(2-pyridyl)pyridinium salts has been demonstrated and investigated. The reaction sequence features a highly regioselective conversion of the N-oxide into its pyridinium salt followed by hydrolytic decomposition of the pyridinium moiety to furnish the 2-aminopyridine product. The method is compatible with a wide range of functional groups, is scalable, and features inexpensive reagents. 15N-labeling results gave products consistent with a Zincke reaction mechanism.

Synthesis and Molecular Docking Studies of N,N-Dimethyl Arylpyranopyrimidinedione Derivatives

The synthesis of N,N-dimethyl arylpyranopyrimidinedione derivatives from aromatic aldehydes, N-methyl-1-(methylthio)-2-nitroethamine (NMSM) and 1,3-dimethyl barbituric acid, in the presence of piperidine as a catalyst, is reported. The reaction mechanism involves a Knoevenagel condensation, followed by Michael addition and intramolecular O-cyclization reaction sequence. The synthesized compounds were docked with human kinesin Eg5 protein to calculate binding energy, inhibition constant and H-bond interaction. All the compounds show good binding affinity towards the protein, with significant docking score.

A C-to-O atom-swapping reaction sequence enabled by Ni-catalyzed decarbonylation of lactones

Advances in site-selective functionalization reactions have enabled single atom changes on the periphery of a complex molecule, but reaction manifolds that enable such changes on the core framework of the...

Synthesis of α- and β-Carbolines by a Metalation/Negishi Cross-Coupling/SNAr Reaction Sequence

Carbolines are considered to be privileged scaffolds in medicinal chemistry. An efficient method for the synthesis of α- and β-carbolines from fluoropyridines and 2-haloanilines is reported. This streamlined procedure consists of a four-step directed ortho-lithiation, zincation, Negishi cross-coupling, and intramolecular nucleophilic aromatic substitution, providing access to a diverse set of functionalized carbolines. While the procedure is applicable to batch conditions, the generation of arylzinc intermediates in continuous flow has been demonstrated.

Divergent Synthesis of Indolenine and Indoline Ring Systems by Palladium-Catalyzed Asymmetric Dearomatization of Indoles

Dearomatized indole derivatives bearing a C3- or C2-stereocenter exist ubiquitously in natural products and biologically active molecules. Despite remarkable advances in their chemical synthesis, stereoselective and regio-divergent methods are still in a high demand. Herein, a Pd-catalyzed intermolecular asymmetric spiroannulation of 2,3-disubstituted indoles with internal alkynes has been developed for the efficient construction of indoline structures with a C2-quaternary stereocenter. Stereospecific aza-semipinacol rearrangement of these indoline derivatives under acidic conditions afforded indolenine products bearing a C3-quaternary stereocenter, where the selectivity for the rearranging group could be controlled by the reaction sequence. The asymmetric spiroannulation together with the subsequent aza-semipinacol rearrangement enabled a divergent access to dearomatized indole derivatives with either a C3- or a C2-quaternary stereocenter.

The Effects of Trace Metal Cations on the High Temperature Reactions of an Halloysite Mineral

<p>This thesis describes a kinetic study of the high temperature solid state reactions of a well characterized halloysite mineral and five of its cation-saturated forms, the cations used being sodium, calcium, manganese, copper and iron (Ill). The reaction sequence may be represented by the idealised equations: The formation of mullite from metakaolinite has been studied in the temperature range 1020° - 1200°C, by X-ray analysis. Comparison of the experimental data with several theoretical models suggests that up to 90% conversion the reaction takes place by exponential nucleation followed by crystal growth. There is, however, some evidence for diffusion occurring as a rate controlling process, especially at high degrees of conversion to mullite. The rate constants and experimental thermodynamic functions have been evaluated for all halloysite samples. The free energies of activation (111-128 k cal.mole-1) and the rate constants are independent of the starting materials, but the enthalpies of activation (51-118 k cal.mole-1) and the entropies of activation (0 to -50 cal.deg.-1 mole-1) are not.</p>

The Effects of Trace Metal Cations on the High Temperature Reactions of an Halloysite Mineral

<p>This thesis describes a kinetic study of the high temperature solid state reactions of a well characterized halloysite mineral and five of its cation-saturated forms, the cations used being sodium, calcium, manganese, copper and iron (Ill). The reaction sequence may be represented by the idealised equations: The formation of mullite from metakaolinite has been studied in the temperature range 1020° - 1200°C, by X-ray analysis. Comparison of the experimental data with several theoretical models suggests that up to 90% conversion the reaction takes place by exponential nucleation followed by crystal growth. There is, however, some evidence for diffusion occurring as a rate controlling process, especially at high degrees of conversion to mullite. The rate constants and experimental thermodynamic functions have been evaluated for all halloysite samples. The free energies of activation (111-128 k cal.mole-1) and the rate constants are independent of the starting materials, but the enthalpies of activation (51-118 k cal.mole-1) and the entropies of activation (0 to -50 cal.deg.-1 mole-1) are not.</p>

Synthesis of Functionalised Cyclohexanes from Carbohydrates

<p>Beta-D-glucopyranose pentaacetate was photobrominated to give the 5-baromide from which 6-deoxy-Beta-D-xylo-hex-5-enopyranose tetraacetate was obtained by reductive elimination. This reaction sequence represents an efficient new route to the 5-ene. A detailed investigation into the photobromination of Beta-D-glucopyranose pentaacetate with bromine and with NBS led to the isolation of several by-products containing bromine substituents at C-1 and/or C-5; their reactions with zinc-acetic acid were studied, and the conformations. in solution of four alkenes derived from the 5-bromo compound were determined. 2,3,4-Triacylated 2,3,4,5-tetrahydroxycyclohexanones were Obtained by mercury (II) catalysed rearrangement of 5-deoxyhex-5-enopyranose esters. The mechanism of this rearrangement, and some enopyranose esters The mechanism of this rearrangement, reactions of the products were examined. The use of these new carbocyclic compounds in the synthesis of branched-chain cyclitol derivatives was explored. By means of diazomethane or, alternatively, hydrogen cyanide, substituted cyclohexanes with one-carbon branches and tertiary hydroxyl groups at the site of chain-branching were preared. Attempts to eliminate water from these tertiary alcohols to give substituted cyclohexene-carbonitriles or -carbaldehydes were unsuccessful.</p>