The tandem gold(I)-catalyzed rearrangement/Nazarov reaction of enynyl acetates in which the double bond is embedded in a piperidine ring was computationally and experimentally studied. The theoretical calculations predict that the position of the propargylic acetate substituent has a great impact on the reactivity. In contrast to our previous successful cyclization of the 2-substituted substrates, where the nitrogen favors the formation of the cyclized final product, the substitution at position 3 was computed to have a deleterious effect on the electronic properties of the molecules, increasing the activation barriers of the Nazarov reaction. The sluggish reactivity of 3-substituted piperidines predicted by the calculations was further confirmed by the results obtained with some designed substrates.

中文翻译：

---

N-杂环的五环化通过串联金催化的炔丙酯衍生物的[3,3]-重排/纳扎罗夫反应：氮原子关键作用的计算研究


通过计算和实验研究了双键嵌入哌啶环的乙酸烯炔酯的串联金（I）催化重排/纳扎罗夫反应。理论计算预测乙酸炔丙酯取代基的位置对反应活性有很大影响。与我们之前成功的 2 位取代底物环化相反，其中氮有利于环化最终产物的形成，计算出 3 位取代对分子的电子性质产生有害影响，增加了活化势垒纳扎罗夫反应。通过计算预测的 3-取代哌啶的缓慢反应性被一些设计的底物获得的结果进一步证实。