Department of Chemistry, University of San Francisco, 2130 Fulton Street, San Francisco, California 94117, USA.
Org Lett. 2010 Mar 5;12(5):972-5. doi: 10.1021/ol100025j.
Mechanisms linking dihydrooctalenes and the corresponding [14]annulene isomers have been investigated computationally. CCSD(T)/cc-pVDZ//BHLYP/6-31G* calculations suggest that the cis/trans isomerization steps required by these mechanisms can occur with reasonable activation barriers by pi-bond shifting, in some cases with two-twist topology, and in others in a planar but nondegenerate fashion. In addition, numerous Mobius conformational minima were located for [14]annulene isomers directly related to the mechanisms studied.
已通过计算研究了二氢辛烯与相应的[14]轮烯异构体之间的连接机制。CCSD(T)/cc-pVDZ//BHLYP/6-31G*计算表明，这些机制所需的顺/反异构化步骤可以通过π键迁移以合理的活化能发生，在某些情况下具有双扭转拓扑结构，而在其他情况下则以平面但非简并的方式发生。此外，还为与所研究的机制直接相关的[14]轮烯异构体定位了许多莫比乌斯构象极小值。
