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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 10, Number 1
BKCSDE 10(1)
January 20, 1989 

 
Title
Catalytic Isomerization of Allyic Alcohols to Carbonyl Compounds with Rh(ClO4)(CO)(PPh3)2 and [Rh(CO)(PPh3)3]ClO4
Author
Chong Shik Chin*, Jeonghan Park, Choongil Kim
Keywords
Abstract
Four coordinated rhodium(Ⅰ) complexes, Rh(ClO4)(CO)(PPh3)2 (1) and [Rh(CO)(PPh3)3]ClO4 (2) catalyze the iosmerization of allylic alcohols to the corresponding carbonyl compounds at room temperature under nitrogen. The isomerization is faster with 2 than with 1, which is understood in terms of relative ease of the last step of the catalytic cycle, the reductive elimination of enol. Relative rates of the isomerization with 1 and 2 for different allylic alcohols are also explained by the relative ease of the enol elimination step in part. The first step of the catalytic cycle, the complex formation of the allylic alcohol through the π-system of the olefinic group of the allylic alcohol and the following step, formation of hydridoallyl complex also seem to affect the overall rate of the isomerization.
Page
102 - 103
Full Text
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