Selective mono-alkylation and arylation of aromatic dihalides by palladium-catalyzed cross-coupling with the Grignard and organozinc reagents

Dibromobenzene, dibromothiophenes, dichloro- and dibromopyridine are highly selectively mono-alkylated and arylated with Grignard or organozinc reagents in the presence of palladium complexes as catalysts.     

Silafunctional compounds in organic synthesis. 21. Hydrogen peroxide oxidation of alkenyl(alkoxy)silanes

The carbon-silicon bond in alkenyl(alkoxy)silanes is readily cleaved by hydrogen peroxide to form the corresponding aldehydes, carboxylic acids or ketones, depending upon the nature of the alkenyl group and the reaction conditions.     

Reflection K-matrices of the 19-vertex model and XXZ spin-1 chain with general boundary terms

We derive and classify all solutions of the boundary Yang-Baxter equation (or the reflection equation) for the 19-vertex model associated with . An integrable XXZ spin-1 chain Hamiltonian with general boundary interactions is also obtained.     

A new isoelectric focusing system for fast two-dimensional gel electrophoresis using a low-concentration polyacrylamide gel supported by a loose multifilament string.

A new isoelectric focusing (IEF) system for two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) has been proposed. In this system, a super-soft and tough IEF gel was achieved by casting polyacrylamide gel down to 2.0% T using a loose multifilament string (LMS) of nylon as a gel support. The IEF apparatus for the LMS-gel, fabricated from acrylic boards, had a cooling water chamber, and eliminated the need of electrode solutions by directly connecting the two ends of individual gels to platinum electrodes. The carrier ampholyte-generated pH gradients using the new IEF system was stable over a long duration of time and a wide range of voltages, and the IEF time became shorter using a 2.0% T gel than using a 4.0% T gel. Also, the LMS-gels prepared in different runs exhibited excellent reproducibility. The new IEF system was applied to 2-D PAGE of a chicken skeletal muscle extract, and it was found that the protein loading capacity, protein entry into the LMS-gels, and protein transfer efficiency from the first-dimensional to the second-dimensional gels were significantly improved by using a low-concentration (2.5% T) gel. Also, proteins of high molecular weight of more than 200 kDa were observed in the 2-D maps, and therefore the new IEF system has a very good potential to be applied for fast 2-D PAGE of high molecular-weight proteins.     

Experimental Study on Light Scattering of High Concentration Suspension

To understand the optical properties of living tissue in the NIR range, it appeared informative to investigate the scattering properties of high concentration particle suspension. We measured the angular light scattering of aqueous suspension of 3.5 μmφ polystyrene particles contained in a 60 μm thick cuvette up to 50% volume concentration at 805 nm wavelength using a goniophotometer. We found that the discrepancy between the measurement and the Monte Carlo simulation becomes larger with increased concentration, which is attributable to the phase function change as well as the scattering coefficient change.     

Silyl-titanation of acetylenes and 1,3-dienes

A Ti^IIISi active species, Cp₂TiSiMe₂Ph, is formed either by the reaction of Cp₂TiCl₂ with two equivalents of PhMe₂SiLi or by the reaction of Cp₂TiCl with one equivalent of PhMe₂SiLi. Highly regio- and stereo-selective silyltitanation by this species has been observed with acetylenes and 1,3-dienes.     

Organofluorosilicates in organic synthesis: XV. Reaction of exo- and endo-5-norbornen-2-ylsilyl derivatives with n-bromosuccinimide. Difference in reactivity between hexacoordinate and tetracoordinate silicon compounds

The reactions of potassium 5-norbornen-2-ylpentafluorosilicate (I) and 5-norbornen-2-yltrimethylsilane (II) with NBS were examined. The former reaction gave 3-nortricyclyl bromide (IV) as the only detectable product, arising from the carbon—silicon bond cleavage. The latter reaction, however, gave 3-bromo-1-nortricyclyltrimethylsilane (V) as the major product, resulting from cleavage of the carbon—hydrogen bond α to silicon, together with IV and an unidentified product. GLC-monitoring of the reactions showed the higher reactivity of the norbornenyl derivative having the leaving group in theendo position irrespective of whether the leaving group is SiF₅ or H. Since no inhibition was observed by the addition of hydroquinone in the dark, the reactions have been regarded as homoallylic electrophilic substitutions. A concerted mechanism seems to be consistent with the experimental data. Cleavage of 1-nortricyclyltrimethylsilane by iodine monochloride to give 1-iodonortricyclene has also been studied.     

Asymmetric hydrosilylation of olefins catalyzed by a chiral ferrocenylphosphine-palladium complex. Asymmetric synthesis of optically active alcohols and bromides from olefins

Optically active norbornyl and 1-phenylethyl alcohols and bromides were obtained, respectively, from norbornyl- and 1-phenylethylpentafluorosilicates which were prepared by asymmetric hydrosilylation of norbornene and styrene with trichlorosilane catalyzed by a chiral ferrocenylphosphine-palladium complex followed by treatment with potassium fluoride.