Metal-Mediated Synthesis of Medium-Sized Rings

How easy are the syntheses of allenes

Advances in the chemical synthesis of C-pyranosides/furanosides are summarized, covering the literature from 2000 to 2016. The majority of the methods take advantage of the construction of the glycosidic C—C bond. These C-glycosylation methods are categorized herein in terms of the glycosyl donor precursors, which are commonly used in O-glycoside synthesis and are easily accessible to nonspecialists. They include glycosyl halides, glycals, sugar acetates, sugar lactols, sugar lactones, 1,2-anhydro sugars, thioglycosides/sulfoxides/sulfones, selenoglycosides/telluroglycosides, methyl glycosides, and glycosyl imidates/phosphates. Mechanistically, C-glycosylation reactions can involve glycosyl electrophilic/cationic species, anionic species, radical species, or transition-metal complexes, which are discussed as subcategories under each type of sugar precursor. Moreover, intramolecular rearrangements, such as the Claisen rearrangement, Ramberg–Backlund rearrangement, and 1,2-Wittig rearrangement, which usuall...

Recent Advances in the Chemical Synthesis of C-Glycosides

Molecular iodine-catalyzed one-pot synthesis of 4-substituted-1,4- dihydropyridine derivatives via Hantzsch reaction

Lewis acid-mediated nucleophilic substitution reactions of substituted tetrahydropyran acetates reveal that the conformational preferences of six-membered-ring cations depend significantly upon the electronic nature of the substituent. Nucleophilic substitutions of C-3 and C-4 alkyl-substituted tetrahydropyran acetates proceeded via pseudoequatorially substituted oxocarbenium ions, as would be expected by consideration of steric effects. Substitutions of C-3 and C-4 alkoxy-substituted tetrahydropyran acetates, however, proceeded via pseudoaxially oriented oxocarbenium ions. The unusual selectivities controlled by the alkoxy groups were demonstrated for a range of other heteroatom substituents, including nitrogen, fluorine, chlorine, and bromine. It is believed that the pseudoaxial conformation is preferred in the ground state of the cation because of an electrostatic attraction between the cationic carbon center of the oxocarbenium ion and the heteroatom substituent. This analysis is supported by the observation that selectivity diminishes down the halogen series, which is inconsistent with electron donation as might be expected during anchimeric assistance. The C-2 heteroatom-substituted systems gave moderately high 1,2-cis selectivity, while small alkyl substituents showed no selectivity. Only in the case of the tert-butyl group at C-2 was high 1,2-trans selectivity observed. These studies reinforce the idea that ground-state conformational effects need to be considered along with steric approach considerations.

Stereochemistry of Nucleophilic Substitution Reactions Depending upon Substituent: Evidence for Electrostatic Stabilization of Pseudoaxial Conformers of Oxocarbenium Ions by Heteroatom Substituents

New substituted C-19-andrographolide analogues with potent cytotoxic activities.

Iodine catalyzes C-glycosidation of d-glucal with silylacetylene

Partial synthesis of ciguatoxin (5R)-ABC segment

Preparation of crosslinked copolymer beads based on glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (HEMA), and divinyl benzene for the use of heavy metal adsorption has been investigated. In our study, a series of porous copolymer beads were synthesized by suspension polymerization in the presence of porogens, 1-dodecanol, toluene, and heptane at different dilutions. The effect of the porogens on the surface appearance and the porous structure of copolymer beads was studied by scanning electron microscopy and BET method. Diethylene triamine chelating copolymers were obtained through a reaction between amine groups of diethylene triamine and epoxide pendant groups of GMA. Adsorption isotherm and quantitative analysis for adsorption capacity involving copper, chromium, manganese, cadmium, iron, and zinc ions were investigated using atomic absorption spectrophotometer. The adsorption was a function of types of metal ions, adsorption time, and solution properties including pH and metal concentration. Adsorption equilibrium was achieved in approximately 50 min with a maximum adsorption capacity at pH 5.0. The Langmuir isotherm was found to be well fitted on the adsorption behavior. The maximum metal adsorption capacities in single ion solution in mole basis were in the order Cu(II) > Cr(VI) > Mn(II) > Zn(II) > Cd (II) > Fe(II). It was found that introducing porogen in the polymerization mixture produced the copolymer beads with better adsorption capacity. The maximum Cu(II) adsorption capacity of chelating poly(GMA-co-HEMA) beads were 1.35 mmol/g (85.79 mg/g) measured from the beads prepared in the presence of 1-heptane with 50% dilution. Consecutive adsorption–desorption experiments showed that crosslinked poly(GMA-co-HEMA) micro-beads can be reused almost without any change in the adsorption capacity.

Rungnapha Saeeng

Papers

New substituted C-19-andrographolide analogues with potent cytotoxic activities.

Iodine catalyzes C-glycosidation of d-glucal with silylacetylene

Partial synthesis of ciguatoxin (5R)-ABC segment

Adsorptive features of poly(glycidyl methacrylate- co -hydroxyethyl methacrylate): effect of porogen formulation on heavy metal ion adsorption

Green synthesis and anti-inflammatory studies of a series of 1,1-bis(heteroaryl)alkane derivatives.