کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5270517 | 1385418 | 2014 | 4 صفحه PDF | دانلود رایگان |
Theoretical calculations of the Michael addition of diethylamine, pyrrolidine, and benzylamine to DMAD at the DFT (B3LYP/6-31+Gâ) level indicate that the reaction follows a stepwise mechanism via a zwitterionic intermediate. The reactions have low activation barriers, 13-15 kcal molâ1 and are exothermic, ÎH° = â29 to â44 kcal molâ1. The detailed investigation of the reaction of benzylamine with DMAD reveals participation of the reactant-, transition structure-, and the product-complexes and that the 1,3-prototropic shift occurs through the benzylamine molecule. It also predicts formation of dimethyl 2-(N-benzylimino)butane-1,4-dicarboxylate as one of the products, which has been duly isolated and characterized experimentally.
Journal: Tetrahedron Letters - Volume 55, Issue 15, 9 April 2014, Pages 2504-2507