• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.360-362
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• 1989

Catalytic isomerization of unsaturated alcohols to the corresponding carbonyl compounds with$Rh(ClO_4)(CO)(PPh_3)_2\;(1)\;and\;[Rh(CO)(PPh_3)_3]ClO_4$ (2) is faster under hydrogen (where hydrogenation also occurs to give saturated alcohols) than under nitrogen. The isomerization under hydrogen seems to occur through an alkylhydridorhodium(III) complex which also undergoes reductive elimination to give hydrogenation products, saturated alcohols. The isomerization under hydrogen is faster with 2 than with 1, which is understood by acceleration of the last step, enol formation by $PPh_3$ dissociated from 2 and present in the reaction mixture when 2 is used as catalyst. Relative rates of the isomerization observed for different unsaturated alcohols are interpreted by steric effects of substituted groups and numbers of hydrogens to be abstracted by the rhodium of the intermediate, alkylhydridorhodium(III) to undergo the reductive elimination to give enol which is then rapidly converted into a carbonyl compound. It has been observed that the hydrogenation is relatively significant when reactions occur slowly whereas the isomerization is predominant when reactions proceed rapidly.

• Resources Recycling
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• v.20 no.4
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• pp.36-45
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• 2011

The recovery of platinum group metals (PGMs) from the leach solution of spent auto-catalyst and the wash solution of the leach residue was investigated in the laboratory scale experiments by the cementation process using metal powders as the reductant. In this study, the effect of Al, Mg and Zn powders on the cementation process was particularly examined. Aluminum powder was selected as the most suitable reductant for the cementation of PGMs. At the cementation time of 10 minute under the aluminium stoichimetric amount of 19.3 and the reaction temperature of $50{\sim}60^{\circ}C$, the recovery of platinum group metals from the leach solution of the spent auto-catalyst was found to be 99.3%, 99.4%, 90.2% for Pt, Pd and Rh, respectively. Under the same conditions with the aluminium stoichimetric amount of 45, the recovery of platinum group metals from the wash solution of the leach residue of spent catalyst was observed to be 97%, 97% and 90% for Pt, Pd and Rh, respectively. In addition, it was possible to upgrade the platinum group metals in the precipitates obtained from the cementation process by about 10% through the removal of metal impurities by the nitric acid leaching at ambient temperature.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2649-2654
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• 2014

Synthesis of north-5'-methylbicyclo[3.1.0]hexyl adenine and hypoxanthine nucleosides with an ethenyl group at C3' position was successfully achieved by a highly facile method. Methylbicyclo[3.1.0]hexanone (${\pm}$)-7 with three contiguous chiral centers and its epimer (${\pm}$)-6 was remarkably simply constructed only by four steps involving a carbenoid insertion reaction in the presence of rhodium (II) acetate dimer as a metal catalyst, giving a correct relative stereochemistry of the generated three chiral centers. Due to steric hindrance from the concave face of the bicyclo[3.1.0]hexanone system, a Grignard reaction of (${\pm}$)-7 with ethenylmagnesium bromide showed exclusive diastereoselectivity towards the b-face. The Grignard reaction chemoselectively proceeded without reacting with ester functionality. Coupling reaction of glycosyl donor (${\pm}$)-11 with 6-chloropurine nucleobase afforded only the desired $N^9$-alkylated nucleoside without the formation of $N^7$-regioisomer. By the conventional method, 6-chloro group was converted into 6-amino and 6-hydroxy groups to give the desired adenine and hypoxanthine bicyclo[3.1.0]hexyl carbanucleosides with 3'-ethenyl group, respectively.