An MO calculation of the reaction path of a symmetry-disfavored 1,3-sigmatropic rearrangement.
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概要
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The path of suprafacial 1,3-sigmatropic rearrangement is studied with the INDO-CI and INDO LMO methods. The methyl migration has been found to be represented by successive 1,2-shifts with a biradicaloid transition state. The interaction between the singly occupied MO's of allyl and methyl fragments is suggested to be responsible for the determination of the path. A subsidiary orbital also plays a part. On the other hand, the chlorine migration has been shown to be a direct 1,3-shift. The interaction between the lowest unoccupied MO of the allyl cationic part and the highest occupied MO of the remaining part, chloride anion, has been found to govern the path of chlorine migration. The lone pair electrons of the migrating fragment makes the successive 1,2-shifts quite unlikely in the 1,3-suprafacial chlorine rearrangements.
- 公益社団法人 日本化学会の論文
著者
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Fukui Kenichi
Faculty of Engineeering Kyoto University
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Fujimoto Hiroshi
Faculty of Engineering, Kyoto University
-
Minato Tsutomu
Faculty of Engineering, Kyoto University
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Inagaki Satoshi
Faculty of Engineering, Kyoto University
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- An MO calculation of the reaction path of a symmetry-disfavored 1,3-sigmatropic rearrangement.