CONFIGURATION INTERACTION AND ORGANIC REACTIVITY .3. SIGMATROPIC REACTIONS AND IONIC REARRANGEMENTS
CONFIGURATION INTERACTION AND ORGANIC REACTIVITY .3. SIGMATROPIC REACTIONS AND IONIC REARRANGEMENTS
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DOI：
10.1021/ja00785a035
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发表时间：
1973-01-01
影响因子：
15
通讯作者：
EPIOTIS, ND
中科院分区：
文献类型：
--
作者：
EPIOTIS, ND
用简单的分子轨道方法研究了构型相互作用对σ转移反应立体选择性的影响。结果表明，当迁移骨架和迁移基团极性相差很大时，构型相互作用可以逆转1，3 σ迁移的立体选择性。另一方面，构型相互作用不能逆转1，5 σ迁移的立体选择性。构型相互作用可以逆转某些1，4阳离子和1，2阴离子重排的立体选择性，但不能逆转1，2阳离子和1，4阴离子重排的立体选择性。与这些预测的实验证据进行了讨论。
Theeffect of configuration interaction on the stereoselectivity of sigmatropic reactions is examined by a simple molecular orbital approach. It is shown that configuration interaction can reverse the stereoselectivity of 1, 3 sigmatropic shifts when the migration framework and the migrating group have widely different polarities. On the other hand, configuration interaction cannot reverse the stereoselectivity of 1, 5 sigmatropic shifts. It is also shown that configuration interaction can reverse the stereoselectivity of certain 1, 4 cationic and 1, 2 anionic rearrangements but not that of 1, 2 cationic and 1, 4 anionic rearrangements. Experimental evidence relating to these predictions is discussed.