Rhodium‐Catalyzed Allylation of Aldehydes with Homoallylic Alcohols by Retroallylation and Isomerization to Saturated Ketones with Conventional or Microwave Heating |
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Authors: | Yuto Sumida Yuko Takada Sayuri Hayashi Koji Hirano Hideki Yorimitsu Dr Koichiro Oshima Prof?Dr |
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Institution: | Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto‐daigaku Katsura, Nishikyo, Kyoto 615‐8510, Japan, Fax: (+81)?75‐383‐2438 |
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Abstract: | The treatment of an aldehyde with a tertiary homoallylic alcohol at 100–250 °C in the presence of cesium carbonate and a rhodium catalyst leads to allyl transfer from the homoallylic alcohol to the aldehyde. The process includes Rh‐mediated retroallylation to form an allyl rhodium species as the key intermediate. The homoallylic alcohol formed initially through allyl transfer is converted under the reaction conditions into the corresponding saturated ketone when bulky ligands are used. Microwave heating at 250 °C accelerates the reaction significantly. |
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Keywords: | allylation C?C activation isomerization retro reactions rhodium |
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