Nonclassical 21-Homododecahedryl Cation Rearrangement Revisited

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• 作者：Said Jalife ; Sukanta Mondal ; Edison Osorio ; José Luis Cabellos ; Gerardo Martínez-Guajardo ; María A. Fernández-Herrera ; Gabriel Merino
• 刊名：Organic Letters
• 出版年：2016
• 出版时间：March 4, 2016
• 年：2016
• 卷：18
• 期：5
• 页码：1140-1142
• 全文大小：262K
• ISSN：1523-7052

文摘

The degenerate rearrangement in the 21-homododecahedryl cation (1) has been studied via density functional theory computations and Born–Oppenheimer Molecular Dynamics simulations. Compound 1 can be described as a highly fluxional hyperconjugated carbocation. Complete scrambling of 1 can be achieved by the combination of two unveiled barrierless processes. The first one is a “rotation” of one of the six-membered rings via a 0.8 kcal·mol^–1 barrier, and the second one is a slower interconvertion between two hyperconjomers via an out-of-plane methine bending (ΔG^⧧ = 4.0 kcal·mol^–1).