Nonstatistical Dynamic Effects in the Thermal C2鈥揅6 Diels鈥揂lder Cyclization of Enyne鈥揂llenes

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• 作者：Debabrata Samanta ; Mehmet Emin Cinar ; Kalpataru Das ; Michael Schmittel
• 刊名：The Journal of Organic Chemistry
• 出版年：2013
• 出版时间：February 15, 2013
• 年：2013
• 卷：78
• 期：4
• 页码：1451-1462
• 全文大小：604K
• 年卷期：v.78,no.4(February 15, 2013)
• ISSN：1520-6904

文摘

The Diels鈥揂lder (DA) reaction channel of the thermal C²鈥揅⁶ (Schmittel) cyclization of enyne鈥揳llenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C²鈥揅⁶/DA cyclization steering it either to a stepwise or a concerted course. Temperature independent product ratios, selectivity of product formation, and computational results obtained at (U)BLYP/6-31G(d) level unveil a mechanism that is strongly controlled by nonstatistical dynamics.