Despite the myriad of selective enzymatic reactions that occur in water, chemists have rarely capitalized on the unique properties of this medium to govern selectivity in reactions. Here we report detailed mechanistic investigations of a water-promoted reaction that displays high selectivity for what is generally a disfavored product. A combination of structural and kinetic data indicates not o...

The 1,2-(CH2 P(1-adamantyl)2 )2 C6 H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2 ] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96 %) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH...

Cholapod anion receptors can achieve high affinities while maintaining compatibility with nonpolar media. Previously they have been shown to transport anions across cell and vesicle membranes. In the present work, the scope of the architecture is expanded and structure-selectivity relationships are investigated. Eight new receptors have been synthesized, with up to six H-bond donor centers. Usi...

the use of methanesulfonic acid as a brønsted acid for direct ortho-acylation of phenols and naphthols proves to be a convenient, more general and direct route to various hydroxyaryl ketones. the route is regioselective, leading to ortho c-acylated products in satisfactory to high yields in most cases. the solvent free reactions described below exhibited environmentally benign in terms of faste...

1,1-diacetates(acylals) were prepared by direct condensation of various aldehydes with acetic anhydride using dipyridine cobalt chloride (copy2cl2) as an efficient and green catalyst under solvent-free conditions at room temperature. the important features of this catalyst method are that the catalyst is solid, stable at high temperatures, soluble in water, stable in air, immiscible in common o...

Ce-modified mesoporous silica materials MCM-41 and SBA-15, namely 32 wt % Ce-Si-MCM-41, 16 wt % Ce-H-MCM-41 and 20 wt % Ce-Si-SBA-15, were prepared, characterized and studied in the selective preparation of trans-carveol by α-pinene oxide isomerization. The characterizations of these catalysts were performed using scanning electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorpti...

Three new solvent-induced metal-organic frameworks (MOFs)-[Cd(H2L)(H2O)3]·NMP (), [Cd3(L)(H2O)4(OH)2] () and [Cd(L)0.5(H2O)]·H2O ()-were designed and successfully prepared via solvothermal reaction by multidentate phenyltetracarboxylic acid [1,1':4',1''-terphenyl]-2',3,3'',5'-tetracarboxylic acid (H4L) and Cd(ii) salts in various solvent systems. Structural analyses indicated that the H2L/L lig...

The effect of carbon dioxide (CO2) sorption on the lower critical solution temperatures of deuterated polybutadiene/polyisoprene blends was determined with in situ small-angle neutron scattering. CO2 was a poor solvent for both polymers and exhibited very weak selectivity between the blend components. The sorption of modest concentrations of CO2, at pressures up to 160 bar, induced phase segreg...

The oxidation of alcohols to carbonyl compounds in a clean fashion (i.e., with water as a solvent or under solvent-free conditions, and using O2 or H2O2 as the primary oxidant) is the subject of considerable research efforts. A new approach for the selective oxidation of soluble aromatic alcohols in water under mild conditions via a novel composite photocatalyst has been developed. The catalyst...

A process to immobilize para-methylbenzoyl cellulose (PMBC) on silica gel has been developed and applied to prepare chiral stationary phases (CSPs) for enantioselective chromatography. The immobilization was achieved by simple irradiation of the polysaccharide derivative with ultraviolet light after coating on a silica gel support. The influence of parameters such as irradiation time and solven...