Nonstatistical Dynamics in the Thermal Garratt鈥揃raverman/[1,5]-H Shift of One Ene鈥揹iallene: An Experimental and Computational Study

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• 作者：Debabrata Samanta ; Anup Rana ; Michael Schmittel
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：September 5, 2014
• 年：2014
• 卷：79
• 期：17
• 页码：8435-8439
• 全文大小：341K
• ISSN：1520-6904

文摘

A mechanistic study of the thermal Garratt鈥揃raverman/[1,5]-H shift of ene鈥揹iallene 6 leading to alkenes (E)-8 and (Z)-8 is reported. The product ratio was found to be temperature-independent and does not agree with the computed energy barriers (i.e., TS2_E^猝?/b> and TS2_Z^猝?/b>). On the basis of experimental and DFT computational results, we propose a mechanism that is strongly controlled by nonstatistical dynamic effects.