Total synthesis of (−)-funebrine via Au-catalyzed regio- and stereoselective γ-butyrolactonization of allenylsilane

The stereoselective total synthesis of (−)-funebrine from 2-butyn-1-ol was described. The crucial steps in the synthesis involved the stereoselective enolate Claisen rearrangement of the (S)-α-acyloxy-α-alkynylsilane 8, the Au-catalyzed regio- and stereoselective lactonization of the allenylsilane 7, and the Paal-Knorr pyrrole condensation using an unsymmetrical 1,4-diketone 4b.     

Carbon Monoxide Oxidation by Polyoxometalate‐Supported Gold Nanoparticulate Catalysts: Activity,Stability, and Temperature‐ Dependent Activation Properties

Nanoparticulate gold supported on a Keggin‐type polyoxometalate (POM), Cs₄[α‐SiW₁₂O₄₀]?n H₂O, was prepared by the sol immobilization method. The size of the gold nanoparticles (NPs) was approximately 2 nm, which was almost the same as the size of the gold colloid precursor. Deposition of gold NPs smaller than 2 nm onto POM (Au/POM) was essential for a high catalytic activity for CO oxidation. The temperature for 50 % CO conversion was ?67 °C. The catalyst showed extremely high stability for at least one month at 0 °C with full conversion. The catalytic activity and the reaction mechanism drastically changed at temperatures higher than 40 °C, showing a unique behavior called a U‐shaped curve. It was revealed by IR measurement that Au^δ+ was a CO adsorption site and that adsorbed water promoted CO oxidation for the Au/POM catalyst. This is the first report on CO oxidation utilizing Au/POMs catalysts, and there is a potential for expansion to various gas‐phase reactions.     

Femtosecond Diffuse-Reflectance Spectroscopy of Various Commercially Available TiO2 Powders

The transient absorption properties of several commercially available TiO₂ photocatalysts were investigated by femtosecond diffuse-reflectance spectroscopy. Using femtosecond diffuse-reflectance spectroscopy, the quantities and rates of the initial trapping processes of holes and electrons generated by the photoexcitation of TiO₂ photocatalysts were investigated. It was found that the total amounts of trapped electrons for the pure-anatase and pure-rutile TiO₂ became smaller with increasing particle size, but increased again when the particles’ diameters were larger than 50 nm. The anatase–rutile mixed TiO₂ photocatalysts were found to have smaller amounts of trapped electrons compared with pure-anatase and pure-rutile TiO₂ photocatalysts. The lifetimes of trapped holes of various TiO₂ photocatalysts were also investigated, and it was found that the lifetimes were proportional to the anatase–rutile mixed ratios.     

Multiple-scattering approach to Sn L3-edge X-ray absorption near-edge structure (XANES) analyses for organic tin compounds

We apply multiple-scattering calculations to the analyses of Sn L₃-edge X-ray absorption near-edge structure (XANES) spectra for environmental organotin compounds such as SnCl_4−nMe_n, SnCl_4−nBt_n, and SnCl_4−nPh_n (n = 0–4) where Me = CH₃, Bt = C₄H₉, and Ph = C₆H₅. The XANES peak at 3960 eV has rich information on the local structure. Referring to the optimized structures by density functional theory (DFT) calculations, multiple-scattering calculations well explain the observed spectral changes for different “organic extents”. The present study also supports the widely-used semiempirical rule called ‘Natoli’s rule’ for these environmental compounds, which will be useful to use XANES spectra for the practical analytical tools.     

Catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates using a phase-transfer catalyst

The catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a β-lactam derivative were synthesized.     

Rod-like liquid crystals of organic transition metal complexes. I. Reversible transformation between blue smectogen and red nematogen

Two novel types of transition-metal-containing liquid crystals, bis(p-n-koxydithiobenzoato)nickel(II) (abbreviated as (C_nO-DTB)₂Ni), and (p-n-alkoxydithiobenzoato)(p-n-alkoxyperthiobenzoato)nickel(II) (abbreviated as (C_nO-DTB)(C_nO-PTB)Ni), were synthesized. It was found that the (C_nO-DTB)₂Ni complex for n = 8 has smectic H and C mesophases, and that the (C_nO-DTB)₂Ni complexes for n = 4 and 8 easily transform into the corresponding monoperthio complexes, _nO-PTB)Ni, by heating at temperatures between 230°C and 285°C. It was confirmed that the transformation originates from an intermolecular reaction between the (C_nO-DTB)₂Ni complexes at high temperatures, and that the origin of the extra sulphurs in the resulting (C_nO-DTB)(C_nO-PTB)Ni complexes is the neighbouring (C_nO-DTB)₂Ni complexes. Interestingly, each of the (C_nO-DTB)(C_nO-PTB)Ni complexes (n = 4 and 8), has nematic mesophase and exhibits a unique double melting behaviour via the nematic phase, which is the first example in liquid crystals. The reversible transformation between the blue smectic rod-like (C_nO-DTB)₂Ni complex and the red nematic Λ-like (C_nO-DTB)(C_nO-PTB)Ni complex is possible.