Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Theoretical Studies on the Gas-Phase Wittig-Oxy-Cope Rearrangement of Deprotonated Diallyl Ether

  • Published : 1991.12.20
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Abstract

The Wittig-oxy-Cope rearrangements of deprotonated diallyl ether, I, $CH_2={\bar{C}}H-CH-O-CH_2-CH=CH_2$, have been investigated theoretically by the AM1 method. A two step mechanism forming a Wittig product ion, II, $(CH_2=CH)$ $(CH_2=CH-CH_2)$ $CHO^-$, through a radical-pair intermediate was found to provide the most favored reaction pathway in the Wittig rearrangement. The subsequent oxy-Cope rearrangement from species II also involves a two step mechanism through a biradicaloid intermediate. The intramolecular proton transfer in I (to form $CH_2=CH-CH_2-O-{\bar{C}}H-CH=CH_2$) is a higher activation energy barrier process compared to the Wittig and oxy-Cope rearrangements and is considered to be insignificant. These results are in good agreement with the condensed-phase as well as gas-phase experimental results.

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