An assembled complex of palladium and non-cross-linked amphiphilic polymer: a highly active and recyclable catalyst for the Suzuki-Miyaura reaction

An insoluble and assembled catalyst of palladium and a non-cross-linked amphiphilic polymer were developed. In the presence of 50-500 ppm mol equiv of catalyst, the Suzuki-Miyaura reaction proceeded efficiently under organic solvent-free conditions. The catalyst was reused 10 times without any decrease in activity and was recycled without any special treatment.[structure: see text]     

Novel synthesis of L-ribose from D-mannono-1,4-lactone

[reaction: see text] D-Mannono-1,4-lactone was efficiently converted into L-ribose in eight steps. A key step of this synthesis is the cyclization of a gamma-hydroxyalkoxamate under Mitsunobu conditions. It is noteworthy that the O-alkylation product was obtained in 94% yield and that none of the N-alkylation product was detected in this cyclization.     

A Cu(II)-mediated C-H oxygenation of sterically hindered tripyridine ligands to form triangular Cu(II)3 complexes

Two sterically hindered tris-pyridyl methane ligands, tris(6-methyl-2-pyridyl)methane (L1) and bis(6-methyl-2-pyridyl)pyridylmethane (L2), are newly synthesized. Under aerobic conditions, Ln (n = 1 or 2) reacts with CuX2 (X = Cl or Br), oxygenated at the methine position to LnOH or LnOMe. The former alcoholate ligand creates trinuclear Cu(II) complexes [Cu3(X)(LnO)3](PF6)2 [(X, n) = (Br, 1) 1, (C1, 1) 2, (Br, 2) 3, or (C1, 2) 4] in which the alkoxide oxygen atoms bridge copper centers. The crystal structures of 1-4 are presented along with their magnetic susceptibility data. The weak antiferromagnetic coupling between the Cu(II) centers in this trinuclear arrangement is due to weak interaction of the magnetic orbitals (dz2) which are oriented along three alternate sides in a hexagon of the Cu3O3 core in 1-4. Under anaerobic conditions, L1 reacts with CuBr2 to form a square pyramidal complex [CuL1Br2] (9) with the ligand facially capping. [Cu(Br)2(L1OMe)] (10) was obtained after the suspension of 9 in MeOH was stirred under air for 48 h. In the presence of cyclohexene, 9 is converted to [Cu(Br)(L1)]m (m = 1 or 2) 5 quantitatively to give trans- 1,2-dibromocyclohexane, indicating that Br2 is generated during the reaction. The FAB MS spectrum of [18O]-1 prepared by the reaction of L1 with CuBr2 under 18O2 shows that the ligand of [18O]-1 is L1(18O-.) L1(18OH), L1OCD3, and bis(6-methyl-2-pyridyl) ketone were obtained from reaction of L1 with CuBr2 in CD3OD under 18O2. These results indicate that the origins of the O atom in L1OH and L1OMe are O2 and MeOH, respectively. On the basis of these results, a mechanism of the oxygenation of L1 in the present system will be proposed.     

Molecular vibrations and force fields of alkyl sulfides: Part XV. C-S stretching vibrations of aliphatic alkyl sulfides

The C-S stretching vibrations of 28 aliphatic sulfides including one thiol are summarized, and all of the C-S stretching bands are classified into several groups. An extraordinarily low frequency associated with the ethyl group is discussed briefly.     

Effect of sonication on the photo-catalytic mineralization of some chlorinated organic compounds

Effects of the irradiation of ultrasound (US) on the photo-catalytic mineralization of some chlorinated organic compounds such as dichloroethane, tri- and tetrachloroethylenes, chloroacetic acids and chloromethanes were examined in oxygen saturated aqueous solutions suspended titanium dioxide (P25) particles. The yields of the sonochemical mineralization for these compounds were found to be extremely low compared to the photo-catalysis. However, the pre-sonication, US irradiation on the sample solution before the photo-irradiation, enhanced significantly the following photo-catalytic degradation to the complete oxidation. The effect was investigated in detail and it was found that the effect was mainly owing to the increase in the capability of the catalysis of which particles were sparsely dispersed by the sonication. The other contribution of the pre-sonication effect was found to be "pre-sonolysis", the initial formation of some intermediated products sonochemically, which are oxidizable more rapidly further to carbon dioxide than the original compound by the following photo-catalytic reactions. The pre-sonolysis effect was observed remarkably for trichloroacetic acid and tetrachloromethane, both of which are known to be hardly reactive to the photo-catalytic degradation. The photo-catalytic degradation with simultaneous sonication were also carried out for these compounds. The synergetic effect in the mineralization was observed both for carbontetrachloride and for trichloroacetic acid, the higher carbon dioxide yield being obtained in the simultaneous reaction than the sum of the yields in the photo-catalysis and the sonolysis each alone, while no significant synergetic effect was observed in the mineralization of other compounds.     

Human hand moves proactively to the external stimulus: an evolutional strategy for minimizing transient error

We investigated particularly the proactive nature of the visual-motor system by steady and transient experiments of a hand-tracking task, and confirmed that the hand motion precedes on the average the target motion in steady runs within a finite frequency range of the sinusoidal target motion. The question why and how much the hand motion should precede was answered by frequency-jump experiments. The results implied that the positive phase shift of the hand motion represents the proactive nature of the visual-motor control system which is adaptationally developed for each person to minimize the transient error of the hand motion when the target motion changes unexpectedly.     

Parametric decomposition of powers of ideals versus regularity of sequences

Let be an ideal in a Noetherian local ring . Then the sequence is -regular if every is a non-zerodivisor in and if for all integers , where runs over the elements of the set .