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Kazuhiko Yokota

Publications and source records attributed to Kazuhiko Yokota.

4 recordsLinked to original sources

Polymer-nanoparticle complexes: from dilute solution to solid state.

We report on the formation and the structural properties of "supermicellar" aggregates made from mineral nanoparticles and polyelectrolyte-neutral block copolymers in aqueous solutions. The mineral particles put under scrutiny are ultrafine and positively charged yttrium hydroxyacetate nanoparticles. Combining light, neutron, and X-ray scattering experiments, we have characterized the sizes and the aggregation numbers of the organic-inorganic complexes. We have found that the hybrid aggregates have typical sizes in the range of 100 nm and exhibit a remarkable colloidal stability with respect to ionic strength and concentration variations. Solid films with thicknesses up to several hundreds of micrometers were cast from solutions, resulting in a bulk polymer matrix in which nanoparticle clusters are dispersed and immobilized. It was found in addition that the structure of the complexes remains practically unchanged during film casting.

Acetates↗

Chelation-assisted transformation: synthesis of 1,4-dicarboxylate esters by the Rh-catalyzed carbonylation of internal alkynes with pyridin-2-ylmethanol.

The reaction of internal alkynes 1 with CO and pyridin-2-ylmethanol (2) in the presence of Rh(4)(CO)(12) results in a double-hydroesterification leading to 1,4-dicarboxylate esters 3. The reaction does not proceed via two consecutive hydroesterifications of alkynes, but the intermediacy of ketene intermediates is proposed. The coordination of the pyridine nitrogen in 2 to rhodium is essential for the reaction to proceed. [reaction: see text]

Journal Article↗

Catalytic cross-coupling reaction of esters with organoboron compounds and decarbonylative reduction of esters with HCOONH4: a new route to acyl transition metal complexes through the cleavage of acyl-oxygen bonds in esters.

The Ru3(CO)12-catalyed cross-coupling reaction of esters with organoboron compounds leading to ketones is described. A wide variety of functional groups can be tolerated under the reaction conditions. Aromatic boronates function as a coupling partner to give aryl ketones. Acyl-alkyl coupling to dialkyl ketones is also achieved by the use of 9-alkyl-9-BBN in place of boronates. The Ru3(CO)12-catalyzed decarbonylative reduction of esters with ammonium formate (HCOONH4) leading to hydrocarbons is also described. No expected aldehydes are produced, and controlled experiments indicate that aldehydes are not intermediate for the transformation. A hydrosilane can also be used as a reducing reagent in place of HCOONH4. A wide variety of functional groups are compatible for both reactions. The key step for both catalytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.

Journal Article↗