Alkylation of catechol with methanol to guaiacol over sulphate-modified zirconia solid acid catalysts

A series of sulphate-promoted ZrO₂ solid acid catalysts with different contents of SO₄ ²⁻ were calcined at 450°C in air for 4 h and tested for the liquid-phase alkylation of catechol to guaiacol in a fixed-bed down-flow reactor. The 5 wt.% SO₄ ²⁻ on ZrO₂ showed the best conversion (82%) and selectivity for guaiacol (84%) at 200°C and 1 bar pressure. A smooth correlation was observed between the catalytical activity and surface acidity of sulphated zirconia. Based on our results, a surface mechanism is proposed.     

Ligand free open air copper(II) mediated aryl formamidation and amination of aryl halides

A simple synthetic procedure for direct formamidation and amination of aryl halides mediated by copper(II) salts was developed in open air, without an external ligand in formamide with potassium carbonate as a base. This approach is particularly efficient when electron active aryl halides are used as substrates. In these cases almost quantitative formamidation was observed.     

Nanostructural organization and anion effects in the optical Kerr effect spectra of binary ionic liquid mixtures

This article reports a study of the effect of anions on the optical Kerr effect (OKE) spectra of binary ionic liquid mixtures with one mixture comprising the 3-methyl-1-pentylimidazolium ([C 5mim] (+)) cation and the anions PF 6 (-) and CF 3CO 2 (-) (TFA (-)), and another mixture comprising the [C 5mim] (+) cation and the anions Br (-) and bis(trifluomethanesulfonyl)imide (NTf 2 (-)). The spectra were obtained by the use of optical heterodyne-detected Raman-induced Kerr Effect Spectroscopy at 295 K. The OKE spectra of the mixtures are compared with the calculated mole-fraction weighted sum of the normalized OKE spectra of the neat liquids. The OKE spectra are nearly additive for [C 5mim]Br/[C 5mim][NTf 2] mixtures, but nonadditive for [C 5mim][PF 6]/[C 5mim][TFA] mixtures. In the case of the equimolar [C 5mim][PF 6]/[C 5mim][TFA] mixture, the nonadditivity is such that the experimental OKE spectrum is narrower than the calculated OKE spectrum. The additivity or nonadditivity of OKE spectra for IL mixtures can be explained by assuming ionic liquids are nanostructurally organized into nonpolar regions and ionic networks. The ionic networks in mixtures will be characterized by "random co-networks" for anions that are nearly the same in size (PF 6 (-) and TFA (-)) and by "block co-networks" for anions that differ greatly in size (Br (-) and NTf 2 (-)).     

Regioselective nucleophilic ring-opening reaction of chiral epoxyallyl alcohols: a ready access to the pyran core of macrolactin 3

Herein we report the synthetic strategy towards the pyran core of macrolactin 3 via Sharpless epoxidation, titanium(IV) mediated regioselective ring-opening reaction of epoxyallyl alcohol/epoxy alcohol and oxa-Michael addition as the key steps.     

Solvent‐assisted anionic ring opening polymerization of glycidol: Toward medium and high molecular weight hyperbranched polyglycerols

Hyperbranched polyglycerols (HPGs) are globular structures with a large number of functionalizable hydroxyl groups and have excellent in vitro and in vivo biocompatibility profiles comparable to polyethylene glycol. This work introduces a facile method for the synthesis of medium molecular weights (M_ws) (50–300 kDa) HPGs, which has been difficult to synthesize with low polydispersity, with the assistance of solvents by ring opening polymerization. The influence of different solvents (1,4‐dioxane, tetrahydropyran (THP), ethylene glycol diethyl ether (EGDE) and decane), solvent to glycidol ratio, concentration of glycidol and the time of polymerization on M_w and polydispersity of HPGs has been studied. The M_w and polydispersity of HPGs are significantly affected by the nature of the polymerization phase (homogeneous or heterogeneous) and chemical structure of the solvent. The differences in the solvation of the potassium cations and change in the nucleophilicity of the alkoxide anion in various solvents may be responsible for the changes in M_w and PDI of the HPG. The M_w of the HPG decreases in the order 1,4‐dioxane > THP > EGDE >decane. The microstructure, solution and thermal properties of the HPG do not depend on the nature of solvent. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2614–2621     

First stereoselective total synthesis of decytospolides A and B

The first synthesis of bioactive decytospolides A and B adopting an oxa-Michael addition as the key step is reported.     

Novel Iodine Reagent System for Regioselective Cleavage of Epoxides to Alcohols

Epoxides are converted regioselectively to corresponding higher substituted alcohols with greater yields using diphosphorus tetraiodide (P₂I₄) as a reducing agent and a catalytic amount of tetraethylammonium bromide at room temperature.     

Perchloric Acid-Catalyzed Synthesis of 9-Aryl Xanthenes-9H-3,6-diol and 1,3,6,8-Tetraol in Water

Efficient syntheses of xanthenes have been described using a catalytic amount of perchloric acid in water. The high temperature and lengthy reaction time normally required for formation of xanthenes derivatives are not necessary when using a catalytic amount of perchloric acid. The method is relatively inexpensive, easily available, nonvolatile, nonexplosive, and thermally robust to catalyze the reaction at 80 °C by simple heating with good to excellent yields. The advantages of the reaction involve simple reaction protocol, simple workup, and improved synthesis in the presence of perchloric acid as catalyst.     

Novel,Mild, and Highly Efficient Method for the Synthesis of 2-Arylbenzothiazoles by the Oxidation of 2-Arylbenzothiazolines with Silicon Lewis Acids

Oxidation of structurally diverse 2-arylbenzothiazolines to give the corresponding 2-arylbenzothiazoles has been carried out in benzene using dimethyldichlorosilane and trimethylchlorosilane. Short reaction times, mild reaction conditions, easy and quick isolation of the products, and excellent yields are the main advantages of this procedure.