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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 13, Number 5
BKCSDE 13(5)
May 20, 1992 

Theoretical Studies of 1,5-Sigmatropic Rearrangements Involving Group Transfer
Ikchoon Lee*, Bon-Su Lee, Nam Doo Kim, Chang Kon Kim
The 1,5-sigmatropic rearrangements involving group (X) migration in ω(x)-substituted 1,3-pentadiene, C1H2=C2H-C3H=C4H-C5H2-X, where X = H, CH3, BH2, NH2, OH or F, are investigated MO theoretically using the AM1 method. For the migrating groups without lone pair electrons, X = H, CH3, or BH2, the suprafacial pathway is favored, whereas for the migrating groups with lone pair electrons participating in the TS, X = NH2, OH, or F, the antarafacial pathway is favored electronically. However excessive steric inhibition in the antarafacial TS for X = NH2 leads to subjacent orbital controlled suprafacial process. The antarafacial shift of F is relatively disfavored compared to that of OH due to smaller orbital overlap and larger interfrontier energy gap in the TS.
565 - 570
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