Mechanistic Information from Nonstationary Points

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• 作者：Anup Rana ; M. Emin Cinar ; Debabrata Samanta ; Michael Schmittel
• 刊名：Organic Letters
• 出版年：2016
• 出版时间：January 4, 2016
• 年：2016
• 卷：18
• 期：1
• 页码：84-87
• 全文大小：368K
• ISSN：1523-7052

文摘

The thermal cyclization of enyne–carbodiimides substituted at both the alkyne and carbodiimide terminus showed two curved Hammett correlations (log k/k₀ against σ_p) that were fully reproduced by DFT (density functional theory) computational results. The latter suggest a concerted mechanism, but the transition state (TS) analysis failed to reveal any mechanistic insight about the reason for a curved Hammett correlation. Instead a preTS inspection, i.e., examination of the electronic and steric details on route between reactant and TS, furnished a detailed picture of the mechanism.