Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes.
Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes.
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DOI：
10.1021/jo302524a
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发表时间：
2013-02
期刊：
影响因子：
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通讯作者：
Debabrata Samanta;M. Cinar;Kalpataru Das;M. Schmittel
中科院分区：
文献类型：
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作者：
Debabrata Samanta;M. Cinar;Kalpataru Das;M. Schmittel
用计算和实验相结合的方法研究了烯-烯烃热C(2)-C(6)(Schmittel)环化反应的Diels-Alder(DA)反应通道，考察了温度对产物比的影响。炔末端的远端取代基影响C(2)-C(6)/DA环化反应的机理，使其分步或协调地进行。在(U)BLYP/6-31G(D)水平上得到的与温度无关的产物比、产物生成的选择性和计算结果揭示了一个由非统计动力学强烈控制的机理。
The Diels-Alder (DA) reaction channel of the thermal C(2)-C(6) (Schmittel) cyclization of enyne-allenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C(2)-C(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.