Bulletin of the Korean Chemical Society

  • 제10권1호
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  • Pages.102-103
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  • 1989
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Catalytic Isomerization of Allyic Alcohols to Carbonyl Compounds with Rh(ClO$_4$)(CO)(PPh$_3)_2$ and [Rh(CO)(PPh$_3)_3$]ClO$_4$

  • 발행 : 19890200
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초록

Four coordinated rhodium(Ⅰ) complexes, Rh($ClO_4$)(CO)$(PPh_3)_2$ and [$Rh(CO)(PPh_3)_3$]$ClO_4$(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 ${\pi}-system$ 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.

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참고문헌

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피인용 문헌

  1. Transposition of Allylic Alcohols into Carbonyl Compounds Mediated by Transition Metal Complexes vol.103, pp.1, 2003, https://doi.org/10.1021/cr0103165