Reductive etherification of carbonyl compounds with alkyl trimethylsilylethers using polymethylhydrosiloxane (PMHS) and catalytic B(C6F5)3

A facile synthesis of symmetrical and unsymmetrical ethers is achieved by reductive coupling of carbonyl compounds with alkoxysilanes. This reaction is performed using inert polymethylhydrosiloxane as the hydride source and B(C₆F₅)₃ as the catalytic activator of the PMHS.     

Simple entry into isonucleosides: synthesis of 6-amino-9-[(3S,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-3-yl]purine

A simple and efficient method for the preparation of isonucleoside 7 is described. The preparation of 1,4-anhydroxylitol 4, a key intermediate, is described by intramolecular cyclization of (2S,3R,4R)-3,5-dibenzyloxypentan-1,2,4-triol 3 using diethyl carbonate and NaH.     

Intermolecular hydroamination of vinyl arenes using tungstophosphoric acid as a simple and efficient catalyst

The intermolecular hydroamination of vinyl arene derivatives has been efficiently carried out using a tungstophosphoric acid (TPA) catalyst under solvent free and mild reaction conditions. The present protocol provides an environmentally benign, easy to handle and highly active solid acid catalyst for hydroamination of vinyl arenes. The catalyst yields both hydroamination and hydroarylation products and the selectivity mostly depends on the reaction conditions.     

Radiolysis of resist polymers. IV. Poly(p-substituted-α-methylstyrene)s

The effect of parasubstituents on the radiation chemistry of poly(α-methylstyrene) (PMS) was compared for the fluoro (PFMS), chloro (PCMS), bromo (PBMS), isopropyl (PiPMS), and methoxy (PMeOM) derivatives. Radiolysis yields, ESR spectra, and GC? MS analysis of products were obtained. PMS and PFMS have similar low radiolysis yields, products, and product distributions. Only main-chain radicals which persist to 200° were observed. PCMS has increased values of G_s, G_x, and G_r. The product analysis results suggest that the presence of chlorine contributes to the primary process by dissociative electron capture and enhances the cleavage of α-methyl group. Irradiation of PBMS caused crosslinking and yielded few volatile products. PMeOMS and PiPMS gel readily by γ-irradiation and may be useful as negative radiation resists.     

Copolymerizations of alkyl methacrylates with vinyltriacetoxysilane

Copolymerizations of methyl methacrylate (MMA) and butyl methacrylate (BMA) with vinyltriacetoxysilane (VTAS) have been carried out in bulk at 70°. The compositions of the copolymers were determined from their silicon contents; the reactivity ratios were calculated by the Kelen-Tüdős method. For MMA/VTAS, r₁ = 7.75 ± 0.31 and for BMA/VTAS, r₁ = 4.62 ± 0.15; in both systems, r₂ is zero, indicating that VTAS does not homopolymerize under the experimental conditions. The influence of the silicon comonomer on properties of the copolymers, such as solubility annd thermal behaviour, was studied.     

Line strengths and transition probabilities for allowed transitions in Fe XXI

Configuration interaction wavefunctions, transition energies, line strengths and transition probabilities for allowed transitions within then=2 complex of C-like Fe XXI have been calculated in the LS coupling scheme. We included internal, semi-internal, and all-external types of correlations. We compare our non-relativistic line strengths values with those of relativistic calculations in the Breit-Pauli approximation. The relativistic effects on line strengths are negligible for all transitions except for the transition¹ D ^e →¹ D ⁰. Experimental wavelengths are used in the calculation of transition probabilities.     

Synthesis of peptides employing Fmoc-amino acid chlorides and commercial zinc dust

Coupling of Fmoc-amino acid chlorides mediated by activated commercial zinc dust for the synthesis of peptides is described. The reaction is carried out in an organic medium. The necessity of using an inorganic base like NaHCO₃/Na₂CO₃ or an organic base like DIEA/NMM/TEA/pyridine is circumvented. The coupling is reasonably fast, clean, racemization free and high yielding.