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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 10, Number 1
BKCSDE 10(1)
January 20, 1989 

Lone Pairs in the 1,3-Sigmatropic Group Rearrangements
Ikchoon Lee*, Jeoung Ki Cho, Bon-Su Lee, Hyuck Keun Oh
Semiempirical computations using the AM1 and MNDO methods were carried out in order to elucidate allowed mechanisms for 1,3-group(X) rearrangement processes with X = BH2, CH3, CN, F, NH2, OH, Cl and SH. The reactivity of the group migration was largely controlled by the steric effect in the 4-membered ring transition state, an antarafacial process having a greater energy barrier due to a greater steric repulsion. For the groups with lone pair electrons, the participation of the lone pair orbital is found to ease the steric effect by enabling the FMO interation with highly polarizable, high lying, lone pair electrons at relatively distant range; the involvement of lone pairs in the transition state causes an alteration of the symmetry selection rule to that of a 6-electron system with an allowed 1,3-suprafacial migration in contrast to an allowed 1,3-antarafacial migration for a 4-electron system. Various stereoelectronic aspects were analysed in some detail.
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