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Lone Pairs in the 1,3-Sigmatropic Group Rearrangements$^1$
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  • Lone Pairs in the 1,3-Sigmatropic Group Rearrangements$^1$
저자명
이익춘,조정기,이본수,오혁근,Lee. Ikchoon,Cho. Jeoung Ki,Lee. Bon-Su,Oh. Hyuck Keun
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1989년|10권 1호|pp.60-66 (7 pages)
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대한화학회
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

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 = $BH_2$, $CH_3$, CN, F, $NH_2$, 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.