Sadayuki Mori

Fine tuning of the orifice size of an open-cage fullerene by placing selenium in the rim: insertion/release of molecular hydrogen

A newly synthesized open-cage fullerene containing selenium in the rim of the 13-membered-ring orifice allows milder conditions for hydrogen insertion, and the rate for hydrogen release is ca. three times faster than its sulfur analogue.

HIGH PRESSURE SYNTHESIS OF CYCLOADDUCT OF FULLERENE C60 WITH 2H-PYRAN-2-ONE

Abstract Under high pressure conditions, fullerene C60 smoothly reacts with 2H-pyran-2-one to give a [4+2] cycloadduct, which can be reduced to an alcohol derivative. ∗∗Presented in part at the 68th Annual Meeting of the Chemical Society of Japan held at Nagoya (October, 1994); Abstract of Papers, p. 352.

Synthesis of oxalate from carbon monoxide and carbon dioxide in thepresence of caesium carbonate

In the presence of caesium carbonate, the direct reaction of CO2 (110 atm) with CO (50 atm) resulted in reductive capture of CO2 to give caesium oxalate in good yield (90.1%) at high temperature (380 °C). The reaction is characteristic of caesium carbonate. When lithium, sodium, potassium and rubidium carbonates were used, oxalate was scarcely produced. The effects of the reaction variables, such as the pressures of CO2 and CO, and the reaction temperature, were examined to optimize the process. From the results of mechanistic studies including a separately examined two-step reaction, 13C-labelling experiments and IR spectroscopic studies of the intermediates, it was concluded that the reaction proceeds through a nucleophilic addition of CO upon the carbonyl carbon of CO2 which is activated by the complexation to caesium carbonate.

Palladium(II)-catalyzed hydroesterification of enol esters: Remarkable α-substituent effect upon regioselectivity

Pd(II)-catalyzed hydroesterification of various enol esters smoothly proceeded upon the combined use of pressurized carbon monoxide and methanol to give the α-or β-acetoxy esters with the regioselectivity highly depending on the size of the α-substituent.

Carbonylation of trichloroacetaldehyde (chloral) in concentrated sulfuric acid: Stereocontrolled synthesis of cis- and trans-2,5-bis(trichloromethyl)-1,3-dioxolan-4-one

Abstract Carbonylation of trichloroacetaldehyde(chloral) in concentrated sulfuric acid readily gave 2,5-bis (trichloromethyl)-1,3-dioxolan-4-ones ( cis and trans ) and 3,3,3-trichloro-2-hydroxypropanoic acid. The cis isomer was isolated for the first time, and confirmed by Xray structural analysis. The cis/trans ratio of dioxolanones largely depended upon the concentration of sulfuric acid. Highly diastereoselective formation of the dioxolanones was achieved with 99wt% sulfuric acid ( cis : trans = 95: 5) or with 90wt% sulfuric acid (0: 100).

Chain carbonylation of methoxymethyl chloride by using agsbf6 catalyst under high pressure of CO

Abstract The chain carbonylation of methoxymethyl chloride ( 1 ) by the use of AgSbF 6 catalyst smoothly proceeded under high pressure of carbon monoxide to give methyl methoxyacetale after treatment with methanol. The reaction was highly dependent on the CO pressure and the reaction temperature, indicating the presence of equilibrium processes. From the temperature dependence of the equilibrium constant, the enthalpy change of the reaction was calculated to be −25.4 kJ mol −1

Novel synthesis of oxalate from carbon dioxide and carbon monoxide in the presence of caesium carbonate

In the presence of caesium carbonate 1, the direct reaction of CO2(110 atm) with CO (20 atm) results in reductive capture of CO2 to give caesium oxalate 2 in good yield at elevated temperature (380 °C).