Radical promoted Wagner-Meerwein-type rearrangement of epoxides in camphoric systems using a Ti(III) radical source

[Chemical reaction: see text] A radical based Wagner-Meerwein-type rearrangement has been observed in camphoric systems. The radical was generated from the epoxide using Cp2TiCl as the radical source. The radical initiator Cp2TiCl was prepared in situ from commercially available Cp2TiCl2 and Zn dust in THF under argon.     

Hydroarylation of alkynes and alkenes through alumina-sulfuric acid catalyzed regioselective CC bond formation

A highly atom-efficient synthetic protocol for hydroarylation of terminal-aryl alkynes and styrene through the regioselective CC bond formation via the electrophilic addition of naphthols and substituted phenols has been developed using alumina-sulfuric acid as a heterogeneous supported solid acid catalyst. This methodology shows excellent regioselectivity and affords the desired product in good to excellent yield. The heterogeneous catalyst can also be recycled efficiently without much loss of activity.     

A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids

Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph₂CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.     

Kinetics of Pu(IV) sorption by smectite-rich natural clay

Kinetics of sorption of Pu(IV) by smectite-rich clay has been studied at varying metal ion concentrations. Different concentrations were achieved using different isotopes of Pu, namely, ²³⁹Pu, ²³⁸Pu and ²³⁷Pu. ²³⁷Pu was produced by alpha induced reaction on ²³⁵U, followed by radiochemical separation of Pu from irradiated U₃O₈ target. The concentrations used are above and below the solubility of Pu(IV) under neutral pH conditions, thereby, indicating the mechanism of sorption reactions of Pu(IV) in typical laboratory experiments and field level observations. Kinetics of Pu(IV) at 10^?13 M concentration was found to be fast whereas at higher metal concentration the rate is governed by a slow step, indicating the role of formation of Pu(IV) polymeric species at the sorbent surface.     

Reducing methane formation in methanol to olefins reaction on metal impregnated SAPO-34 molecular sieve

SAPO-34 silicoaluminophosphate molecular sieve produces large amounts of methane at elevated temperatures in the methanol to olefins (MTO) process. This significantly reduces the lower olefins selectivity a key factor in determining the commercial viability of this catalyst. Impregnation of the SAPO-34 molecular sieve with metal ions such as K, Cs, Pt, Ag and Ce was found to reduce the amount of methane significantly at higher temperatures thereby increasing the lower olefins selectivity. This observed effect is less apparent at lower temperatures where the amount of methane formed is generally low. This revised version was published online in June 2006 with corrections to the Cover Date.     

Gamma irradiation route to synthesis of highly re-dispersible natural polymer capped silver nanoparticles

Aqueous dispersions of highly stable, redispersible silver nanoparticles (Ag NPs) were synthesized using gamma radiolysis with gum acacia as a protecting agent. The formation of nanosized silver was confirmed by its characteristic surface plasmon absorption peak at around 405 nm in UV–vis spectra. The size of the silver nanoparticles can be tuned by controlling the radiation dose, ratio of gum acacia to silver ions and also the ionic strength of the medium. Dynamic light scattering (DLS) measurement of the as-synthesized nanoparticles indicated the size less than 3 nm at higher dose of radiation and this also corroborated the size measurement from the width of the corresponding X-ray diffraction (XRD) peak. The face centered cubic (fcc) crystallinity of the nanoparticles was evident from XRD and high resolution transmission electron microscopic (HRTEM) measurements. Fourier transform infra-red (FTIR) spectroscopic data indicate a bonding of Ag NPs with COO^? group of acacia through bridging bidentate linkage.     

Dioxygen‐Mediated Decarbonylative CH Alkylation of Heteroaromatic Bases with Aldehydes

An operationally simple and economical method for the direct alkylation of heteroaromatic bases employing readily available aldehydes as alkyl radical precursors and molecular oxygen as a reagent is presented. This simple transformation demonstrates a broad substrate scope with respect to aldehydes and nitrogen heterocycles, enabling the introduction of several medicinally important yet challenging alkyl moieties, such as ethyl, isopropyl, tert‐butyl, and cyclohexyl to the different classes of heterocyclic bases in good to excellent yields.