Presset Marc, Rajzmann Michel, Dauvergne Guillaume, Rodriguez Jean, Coquerel Yoann
Aix Marseille Université, CNRS, Centrale Marseille, ISM2, 13397 Marseille, France.
Molecules. 2020 Oct 20;25(20):4811. doi: 10.3390/molecules25204811.
Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.
实验观察到，由热诱导的沃尔夫重排产生的α-氧代烯酮与1-氮杂二烯之间的形式氮杂狄尔斯-阿尔德环加成反应的选择性发生了反转，这是α-氧代烯酮、1-氮杂二烯以及反应温度和时间的函数。还观察到非对映选择性出现了一些意外的反转。利用密度泛函理论（DFT）方法进行的计算建模充分解释了这些选择性的变化。
