Hyperconjugation as it affects conformational analysis |
| |
| Authors: | Christopher J Cramer |
| |
| Institution: | Department of Chemistry and Supercomputer Institute, University of Minnesota, Minneapolis, MN 55455-0431, USA |
| |
| Abstract: | A primer for the qualitative identification and quantitative analysis of hyperconjugative delocalization is presented. The particular focus is upon the influence of hyperconjugation as it affects conformational analysis. Computational methodologies are illustrated within the context of several diverse molecular systems: anomeric and reverse anomeric effects in 2-tetrahydropyranosylammonium, generalized anomeric effects in phosphorus-stabilized carbanions, and hyperconjugative effects in phosphorus- and silicon-based trigonal bipyramids. Hyperconjugation is shown to compete with apicophilicity in the final examples. Although the latter influence has long been accounted for in traditional conformational analysis of trigonal bipyramidal systems, the former has been less appreciated. |
| |
| Keywords: | Hyperconjugation Molecular orbital Ab initio calculation Anomeric effect |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
